Herbicides comprising benzoylcyclohexanediones and safeners

ABSTRACT

Herbicidal compositions are described that comprise active substances from the group of the benzoylcyclohexanediones and also safeners. These herbicidal compositions are especially suitable for use against weed plants in crop plant cultures.

[0001] The invention pertains to the technical field of cropprotectants, especially herbicide/antidote combinations (activesubstance/safener combinations) suitable for use against competing weedplants in crop plant cultures.

[0002] Numerous active herbicidal substances are known to be inhibitorsof the enzyme p-hydroxyphenylpyruvate dioxygenase (HPPD). For instance,Proc. Br. Crop Prot. Conf. Weeds, 1991,1, 51; Proc. Br. Crop Prot. Conf.Weeds, 1995,1, 35 disclose benzoylcyclohexanediones, benzoylpyrazoles,and benzoylisoxazoles of this kind. More recently, further such activesubstances have been disclosed, for example, in WO 00/21924 and WO01/07422.

[0003] As with many other active herbicidal substances, these HPPDinhibitors too are not always sufficiently compatible with (i.e., lacksufficient selectivity for) certain important crop plants, such as corn,rice or cereals, whereby imposing narrow limitations on their use. Insome crops, therefore, they cannot be used, or can be used only at suchlow application rates that the desired broad herbicidal activity towardweed plants is not ensured. More particularly, many of these herbicideslack complete selectivity for weed plants in corn, rice, cereals, sugarcane, and certain other crops.

[0004] A known means for overcoming these disadvantages is to use activeherbicidal substances in combination with a substance known as a safeneror antidote. EP-A 0 943 240, WO 99/66795, and WO 00/30447, for example,describe various combinations of certain HPPD inhibitors with safeners.

[0005] A safener is a compound which eliminates or lessens thephytotoxic properties of a herbicide toward crop plants withoutsubstantially reducing the herbicidal action toward weed plants.

[0006] Identifying a safener for a particular group of herbicides isstill a difficult task, since the precise mechanisms by which a safenerlessens the noxious effect of herbicides are unknown. Consequently, thefact that a compound acts as safener in combination with one particularherbicide does not permit conclusions as to the safener action of such acompound with other groups of herbicides. In the use of safeners toprotect crop plants against herbicide damage, it has been found that thesafeners in many cases may still have certain disadvantages. Theseinclude the following:

[0007] the safener lessens the action of the herbicides toward the weedplants;

[0008] the crop plant protecting properties are inadequate;

[0009] with a given herbicide, the spectrum of crop plants in which thesafener/herbicide combination is to be used is too small;

[0010] a sufficiently large number of herbicides cannot be combined witha given safener.

[0011] It is an object of the present invention to provide furthercombinations of herbicides from the group of the HPPD inhibitors withsafeners that are suitable for raising the selectivity of theseherbicides with respect to important crop plants.

[0012] Novel combinations have now been found of certain herbicides fromthe group of the HPPD inhibitors which carry selected substituents inposition 3 of the benzoyl moiety with numerous other compounds whichraise the selectivity of these herbicides with respect to important cropplants.

[0013] The invention accordingly provides a herbicidally activecomposition comprising

[0014] A) a herbicidally effective amount of one or more compounds ofthe formula (I)

[0015] in which the symbols and indices have the following definitions:

[0016] R¹ is nitro, amino, halogen, cyano, (C₁-C₄)-alkyl,(C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-haloalkyl,(C₂-C₄)-haloalkenyl, (C₂-C₄)-haloalkynyl, (C₁-C₄)-haloalkoxy,(C₁-C₄)-haloalkylthio, (C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylthio, (C₁-C₄)-alkoxy,(C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy, (C₁-C₄)-alkylcarbonyl,(C₁-C₄)-alkylaminosulfonyl, (C₁-C₄)-dialkylaminosulfonyl,(C₁-C₄)-alkylcarbamoyl, (C₁-C₄)-dialkylcarbamoyl,(C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, (C₁-C₄)-alkylamino or(C₁-C₄)-dialkylamino;

[0017] R² is (C₁-C₄)-haloalkoxy-(C₁-C₄)-alkyl,(C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy-(C₁-C₄)— alkoxy-(C₁-C₄)-alkyl,(C₃-C₆)-cycloalkoxy-(C₁-C₄)-alkyl, (C₃-C₆)-cycloalkyl-(C₁-C₄)-alkoxy,tetrahydrofuran-2-yl-methoxy-(C₁-C₄)-alkyl,tetrahydrofuran-3-yl-methoxy-(C₁-C₄)-alkyl or a heterocyclic radicalfrom the group consisting of isoxazol-3-yl and 4,5-dihydroisoxazol-3-ylwhich is substituted by a radical from the group consisting ofcyanomethyl, ethoxymethyl and methoxymethyl;

[0018] R³ is OR⁵, cyano, halogen, cyanato, thiocyanato,(C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfonyl,(C₂-C₄)-alkenylthio, (C₂-C₄)-alkenylsulfinyl, (C₂-C₄)-alkenylsulfonyl,(C₂-C₄)-alkynylthio, (C₂-C₄)-alkynylsulfinyl, (C₂-C₄)-alkynylsulfonyl,(C₁-C₄)-haloalkylthio, (C₂-C₄)-haloalkenylthio, (C₂-C₄)-haloalkynylthio,(C₁-C₄)-haloalkylsulfinyl, (C₂-C₄)-haloalkenylsulfinyl,(C₂-C₄)-haloalkynylsulfinyl, (C₁-C₄)-haloalkylsulfonyl,(C₂-C₄)-haloalkenylsulfonyl or (C₂-C₄)-haloalkynylsulfonyl;

[0019] R⁴ is (C₁-C₄)-alkyl;

[0020] R⁵ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl or(C₁-C₄)-alkoxy-(C₁-C₄)-alkyl;

[0021] a is 0, 1, 2 or 3;

[0022] b is 0, 1 or 2;

[0023] and

[0024] B) an antidote-active amount of one or more compounds from groupsa) to e): a) compounds of the formulae (II) to (IV),

[0025]  in which the symbols and indices have the following definitions:

[0026] n′ is a natural number from 0 to 5, preferably from 0 to 3;

[0027] T is a (C₁- or C₂-)-alkanediyl chain which is unsubstituted orsubstituted by one or two (C₁-C₄)-alkyl radicals or by[(C₁-C₃)-alkoxy]carbonyl;

[0028] W is a radical from the group (W1) to (W4),

[0029] m′ is 0 or 1;

[0030] R¹⁷ and R¹⁹ are identical or different and are halogen,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro or (C₁-C₄)-haloalkyl;

[0031] R¹⁸ and R²⁰ are identical or different and are OR²⁴, SR²⁴ orNR²⁴R²⁵ or a saturated or unsaturated 3- to 7-membered heterocyclecontaining at least one nitrogen atom and up to 3 heteroatoms which isbonded by the nitrogen atom to the carbonyl group in (II) or (III) andis unsubstituted or substituted by radicals from the group consisting of(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and unsubstituted or substituted phenyl,preferably a radical of the formula OR²⁴, NHR²⁵ or N(CH₃)₂, inparticular of the formula OR²⁴;

[0032] R²⁴ is hydrogen or an unsubstituted or substituted aliphatichydrocarbon radical, preferably having a total of from 1 to 18 carbonatoms;

[0033] R²⁵ is hydrogen, (C₁-C₆)-alkyl, (C₁-C₆)-alkoxy or substituted orunsubstituted phenyl;

[0034] R²⁶ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl,(C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, (C₁-C₆)-hydroxyalkyl, (C₃-C₁₂)-cycloalkylor tri-(C₁-C₄)-alkylsilyl;

[0035] R²⁷, R²⁸ and R²⁹ are identical or different and are hydrogen,(C₁-C₈)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₁₂)-cycloalkyl or substituted orunsubstituted phenyl;

[0036] R²¹ is (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-alkenyl,(C₂-C₄)-haloalkenyl, (C₃-C₇)-cycloalkyl, preferably dichloromethyl;

[0037] R²², R²³ are identical or different and are hydrogen,(C₀-C₄)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-haloalkyl,(C₂-C₄)-haloalkenyl, (C₁-C₄)-alkylcarbamoyl-(C₁-C₄)-alkyl,(C₂-C₄)-alkenylcarbamoyl-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,dioxolanyl-(C₁-C₄)-alkyl, thiazolyl, furyl, furylalkyl, thienyl,piperidyl, substituted or unsubstituted phenyl, or R²² and R²³ togetherform a substituted or unsubstituted heterocyclic ring, preferably anoxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidineor benzoxazine ring;

[0038] b) one or more compounds from the following group:

[0039] 1,8-naphthalic anhydride,

[0040] methyl diphenylmethoxyacetate,

[0041] cyanomethoxyimino(phenyl)acetonitrile (cyometrinile),

[0042] 1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil),

[0043] 4′-chloro-2,2,2-trifluoroacetophenone O-1,3-dioxolan-2-ylmethyloxime (fluxofenim),

[0044] 4,6-dichloro-2-phenylpyrimidine (fenclorim),

[0045] benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate(flurazole),

[0046] 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),

[0047] N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),

[0048] 1-[4-(N-2-methoxybenzoylsulfarnoyl)phenyl]-3-methylurea,

[0049] 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,

[0050] 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,

[0051] 1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea,

[0052] (2,4-dichlorophenoxy)acetic acid (2,4-D),

[0053] (4-chlorophenoxy)acetic acid,

[0054] (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),

[0055] 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),

[0056] (4-chloro-o-tolyloxy)acetic acid (MCPA),

[0057] 4-(4-chloro-o-tolyloxy)butyric acid,

[0058] 4-(4-chlorophenoxy)butyric acid,

[0059] 3,6-dichloro-2-methoxybenzoic acid (dicamba),

[0060] 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate(lactidichlor)

[0061] and their salts and esters, preferably (C₁-C₈);

[0062] c) N-acylsulfonamides of the formula (V) and their salts,

[0063] in which

[0064] R³⁰ is hydrogen, a carbon-containing radical such as ahydrocarbon radical, a hydrocarbon-oxy radical, a hydrocarbon-aminoradical, a hydrocarbon-thio radical or a heterocyclyl radical, each ofthe 4 last-mentioned radicals being unsubstituted or being substitutedby one or more identical or different radicals selected from the groupconsisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl,carboxamide, sulfonamide and radicals of the formula —Z^(a)—R^(a), eachhydrocarbon moiety preferably having 1 to 20 carbon atoms and acarbon-containing radical R⁺ inclusive of substituents preferably having1 to 30 carbon atoms;

[0065] R³¹ is hydrogen or (C₁-C₄)-alkyl, preferably hydrogen, or

[0066] R³⁰ and R³¹ together with the group of the formula —CO—N— are theresidue of a 3- to 8-membered saturated or unsaturated ring;

[0067] R³² is identical or different and is halogen, cyano, nitro,amino, hydroxyl, carboxyl, formyl, CONH₂, SO₂NH₂ or a radical of theformula —Z—R^(b);

[0068] R³³ s hydrogen or (C₁-C₄)-alkyl, preferably hydrogen;

[0069] R³⁴ is identical or different and is halogen, cyano, nitro,amino, hydroxyl, carboxyl, CHO, CONH₂, SO₂NH₂ or a radical of theformula —Z^(c)—R^(c);

[0070] R^(a) is a hydrocarbon radical or a heterocyclyl radical, each ofthe two last-mentioned radicals being unsubstituted or substituted byone or more identical or different radicals selected from the groupconsisting of halogen, cyano, nitro, amino, hydroxyl, mono- anddi-[(C₁-C₄)-alkyl]amino, or an alkyl radical in which a plurality,preferably 2 or 3, non-adjacent CH₂ groups are in each case replaced byone oxygen atom;

[0071] R^(b),R^(c) are identical or different and are a hydrocarbonradical or a heterocyclyl radical, each of the two last-mentionedradicals being unsubstituted or substituted by one or more identical ordifferent radicals selected from the group consisting of halogen, cyano,nitro, amino, hydroxyl, phosphoryl, halo-(C₁-C₄)-alkoxy, mono- anddi-[(C₁-C₄)-alkyl]amino, or an alkyl radical in which a plurality,preferably 2 or 3, non-adjacent CH₂ groups are replaced in each case byone oxygen atom;

[0072] Z^(a) is a divalent group of the formula —O—, —S—, —CO—, —CS—,—CO—O—, —CO—S—, —O—CO—, —S—CO—, —SO—, —SO₂—, —NR*—, —CO—NR*—, —NR*—CO—,—SO₂—NR*— or —NR*—SO₂—, the bond given on the right-hand side of each ofthe divalent groups being the bond to the radical R^(a), and theradicals R* in the 5 last-mentioned radicals independently of each otherbeing in each case H, (C₁-C₄)-alkyl or halo-(C₁-C₄)-alkyl;

[0073] Z^(b),Z^(c) independently of one another are a direct bond or adivalent group of the formula —O—, —S—, —CO—, —CS—, —CO—O—, —CO—S—,—O—CO—, —S—CO—, —SO, SO₂—, —NR*—, —SO₂—NR*—, —NR*—SO₂—, —CO—NR*— or—NR*—CO—, the bond given on the right-hand side of each of the divalentgroups being the bond is linked to the radical R^(b) or R^(c) and theradicals R* in the 5 last-mentioned radicals independently of oneanother are in each case H, (C₁-C₄)-alkyl or halo-(C₁-C₄)-alkyl;

[0074] n is an integer from 0 to 4, preferably 0, 1 or 2, in particular0 or 1, and

[0075] m is an integer from 0 to 5, preferably 0, 1, 2 or 3, inparticular 0, 1 or 2;

[0076] d) acylsulfamoylbenzamides of the formula (VI), optionally alsoin salt form,

[0077] in which

[0078] X³ is CH or N;

[0079] R³⁵ is hydrogen, heterocyclyl or a hydrocarbon radical, the twolast-mentioned radicals optionally being substituted by one or moreidentical or different radicals selected from the group consisting ofhalogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH₂, SO₂NH₂ andZ^(a)—R^(a);

[0080] R³⁶ is hydrogen, hydroxyl, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl,(C₂-C₆)-alkynyl, (C₁-C₆)-alkoxy, (C₂-C₆)-alkenyloxy, the fivelast-mentioned radicals optionally being substituted by one or moreidentical or different radicals selected from the group consisting ofhalogen, hydroxyl, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and (C₁-C₄)-alkylthio,or

[0081] R³⁵ and R³⁶together with the nitrogen atom to which they areattached are a 3- to 8-membered saturated or unsaturated ring;

[0082] R³⁷ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO,CONH₂, SO₂NH₂ or Z^(b)—R^(b);

[0083] R³⁸ is hydrogen, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl or(C₂-C₄)-alkynyl;

[0084] R³⁹ is halogen, cyano, nitro, amino, hydroxyl, carboxyl,phosphoryl, CHO, CONH₂, SO₂NH₂ or Z^(c)—R^(c);

[0085] R^(a) is a (C₂-C₂₀)-alkyl radical whose carbon chain isinterrupted once or more than once by oxygen atoms, or is heterocyclylor a hydrocarbon radical, the two last-mentioned radicals optionallybeing substituted by one or more identical or different radicalsselected from the group consisting of halogen, cyano, nitro, amino,hydroxyl, mono- and di-[(C₁-C₄)-alkyl]amino;

[0086] R^(b), R^(c) are identical or different and are a (C₂-C₂₀)-alkylradical whose carbon chain is interrupted once or more than once byoxygen atoms, or a heterocyclyl or a hydrocarbon radical, the twolast-mentioned radicals optionally being substituted by one or moreidentical or different radicals selected from the group consisting ofhalogen, cyano, nitro, amino, hydroxyl, phosphoryl, (C₁-C₄)-haloalkoxy,mono- and di-[(C₁-C₄)-alkyl]amino;

[0087] Z^(a) is a divalent unit selected from the group consisting of O,S, CO, CS, C(O)O, C(O)S, SO, SO₂, NR^(d), C(O)NR^(d) or SO₂NR^(d);

[0088] Z^(b), Z^(c) are identical or different and are a direct bond ora divalent unit selected from the group consisting of O, S, CO, CS,C(O)O, C(O)S, SO, SO₂, NR^(d), SO₂NR^(d) or C(O)NR^(d);

[0089] R^(d) is hydrogen, (C₁-C₄)-alkyl or (C₁-C₄)-haloalkyl;

[0090] r is an integer from 0 to 4, and

[0091] q in the event that X³ is CH, is an integer from 0 to 5 and, inthe event that X is N, is an integer from 0 to 4;

[0092] e) compounds of the formula (VII),

[0093] in which the symbols and indices have the following definitions:

[0094] X is CH or N,

[0095] p in the event that X=N, is an integer from 0 to 2 and, in theevent that X=CH, is an integer from 0 to 3;

[0096] R⁴⁰ is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkoxy, nitro, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-alkoxycarbonyl, phenyl or phenoxy, the two last-mentionedradicals being unsubstituted or substituted by one or more, preferablyup to three, identical or different radicals from the group consistingof halogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy,halo-(C₁-C₄)-alkoxy, nitro and cyano;

[0097] R⁴¹ is hydrogen or (C₁-C₄)-alkyl, and

[0098] R⁴² is hydrogen, (C₁-C₈)-alkyl, (C₃-C₆)-cycloalkyl,(C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl or aryl, each of the aforementionedcarbon-containing radicals being unsubstituted or substituted by one ormore, preferably up to three, identical or different radicals from thegroup consisting of halogen, nitro, cyano, hydroxyl, (C₁-C₈)-alkoxy, inwhich one or more, preferably up to three, CH₂ groups may be replaced byoxygen, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfonyl, (C₃-C₆)-cycloalkyl,(C₂-C₄)-alkenyloxy and (C₂-C₄)-alkynyloxy,

[0099] inclusive of the stereoisomers and the agriculturally customarysalts.

[0100] A herbicidally effective amount is, for the purposes of theinvention, an amount of one or more herbicides which is capable ofadversely affecting plant growth.

[0101] An antidote-active amount is, for the purposes of the invention,an amount of one or more safeners which is capable of at least partiallycountering the phytotoxic effect of a herbicide or herbicide mixture ona crop plant.

[0102] Unless otherwise defined individually, the following definitionsgenerally apply to the radicals in the formulae (I) to (VIII) andsubsequent formulae.

[0103] The radicals alkyl, alkoxy, haloalkyl, haloalkoxy, alkylamino andalkylthio and the corresponding unsaturated and/or substituted radicalscan be in each case straight-chain or branched in the carbon skeleton.Alkyl radicals, also the composite meanings such as alkoxy, haloalkyland the like, preferably have 1 to 4 carbon atoms and are, for example,methyl, ethyl, n- or i-propyl or n-, i-, t- or 2-butyl. Alkenyl andalkynyl radicals have the meanings of the unsaturated radicals which arepossible and which correspond to the alkyl radicals; alkenyl is, forexample, allyl, 1-methylprop-2-en-1-yl, 2-methylprop-2-en-1-yl,but-2-en-1-yl, but-3-en-1-yl, 1-methylbut-3-en-1-yl andI-methylbut-2-en-1-yl. Alkynyl is, for example, propargyl,but-2-yn-1-yl, but-3-yn-1-yl, 1-methylbut-3-yn-1-yl. “(C₁-C₄)-Alkyl” isthe abbreviation for alkyl having 1 to 4 carbon atoms; the same appliesanalogously to other general definitions of radicals, where the rangesof the possible number of carbon atoms are indicated in brackets.

[0104] Cycloalkyl is, preferably, a cyclic alkyl radical having 3 to 8,preferably 3 to 7, especially preferably 3 to 6, carbon atoms, forexample cyclopropyl, cyclobutyl, cyclopentyl and cyclohexyl.Cycloalkenyl and cycloalkynyl denote corresponding unsaturatedcompounds.

[0105] Halogen is fluorine, chlorine, bromine or iodine. Haloalkyl,haloalkenyl and haloalkynyl are alkyl, alkenyl or alkynyl which arepartially or fully substituted by halogen, preferably by fluorine,chlorine and/or bromine, in particular by fluorine or chlorine, forexample CF₃, CHF₂, CH₂F, CF₂CF₃, CH₂FCCIFM, CCl₃, CHCl₂, CH₂CH₂Cl.Haloalkoxy is, for example, OCF₃, OCHF₂, OCH₂F, OCF₂CF₃, OCH₂CF₃ andOCH₂CH₂Cl. This also applies analogously to other halogen-substitutedradicals.

[0106] An aliphatic hydrocarbon radical is generally a straight-chain orbranched saturated or unsaturated hydrocarbon radical, preferably having1 to 18, especially preferably 1 to 12, carbon atoms, for example alkyl,alkenyl or alkynyl. Aryl is generally a mono-, bi- or polycyclicaromatic system having preferably 6 to 14 carbon atoms, for examplephenyl, naphthyl, pentalenyltetrahydronaphthyl, indenyl, indanyl andfluorenyl, especially preferably phenyl. Aliphatic hydrocarbon radicalpreferably means alkyl, alkenyl or alkynyl having up to 12 carbon atoms;the same applies analogously to an aliphatic hydrocarbon radical in ahydrocarbon-oxy radical.

[0107] Heterocyclic ring, heterocyclic radical or heterocyclyl is amono-, bi- or polycyclic ring system which is saturated, unsaturatedand/or aromatic and contains one or more, preferably 1 to 4,heteroatoms, preferably selected from the group consisting of N, S andO. Preferred are saturated heterocycles having 3 to 7 ring atoms and oneor two heteroatoms selected from the group consisting of N, O and S,chalcogens not being adjacent. Especially preferred are monocyclic ringshaving 3 to 7 ring atoms and a heteroatom selected from the groupconsisting of N, O and S, and also morpholine, dioxolane, piperazine,imidazoline and oxazolidine. Very especially preferred saturatedheterocycles are oxirane, pyrrolidone, morpholine and tetrahydrofuran.Also preferred are partially unsaturated heterocycles having 5 to 7 ringatoms and one or two heteroatoms selected from the group consisting ofN, O and S. Especially preferred are partially unsaturated heterocycleshaving 5 to 6 ring atoms and one heteroatom selected from the groupconsisting of N, O and S. Very especially preferred partiallyunsaturated heterocycles are pyrazoline, imidazoline and isoxazoline.Equally preferred are mono- or bicyclic aromatic heterocycles having 5to 6 ring atoms which contain one to four heteroatoms selected from thegroup consisting of N, O, S, chalcogens not being adjacent. Especiallypreferred are monocyclic aromatic heterocycles having 5 to 6 ring atomswhich contain a heteroatom selected from the group consisting of N, Oand S, and also pyrimidine, pyrazine, pyridazine, oxazole, thiazole,thiadiazole, oxadiazole, pyrazole, triazole and isoxazole. Veryespecially preferred are pyrazole, thiazole, triazole and furan.

[0108] Substituted radicals, such as substituted hydrocarbon radicals,for example substituted alkyl, alkenyl, alkynyl, aryl, phenyl andarylalkyl such as benzyl, or substituted heterocyclyl or heteroaryl, area substituted radical which is derived from the unsubstituted parentstructure, the substituents being, by preference, one or more,preferably 1, 2 or 3, in the case of Cl and F also up to the maximumpossible number of, radicals selected from the group consisting ofhalogen, alkoxy, haloalkoxy, alkylthio, hydroxyl, amino, nitro,carboxyl, cyano, azido, alkoxycarbonyl, alkylcarbonyl, formyl,carbamoyl, mono- and dialkylaminocarbonyl, substituted amino such asacylamino, mono- and dialkylamino and alkylsulfinyl, haloalkylsulfinyl,alkylsulfonyl, haloalkylsulfonyl and, in the case of cyclic radicals,also alkyl and haloalkyl and the unsaturated aliphatic radicals whichcorrespond to the abovementioned saturated hydrocarbon-containingsubstituents, preferably alkenyl, alkynyl, alkenyloxy and alkynyloxy. Inthe case of radicals having carbon atoms, those having 1 to 4 carbonatoms, in particular 1 or 2 carbon atoms, are preferred. As a rule,preferred radicals are those selected from the group consisting ofhalogen, for example fluorine or chlorine, (C₁-C₄)-alkyl, preferablymethyl or ethyl, (C₁-C₄)-haloalkyl, preferably trifluoromethyl,(C₁-C₄)-alkoxy, preferably methoxy or ethoxy, (C₁-C₄)-haloalkoxy, nitroand cyano. Especially preferred in this context are the substituentsmethyl, methoxy and chlorine.

[0109] Mono- or disubstituted amino is a chemically stable radicalselected from the group of the substituted amino radicals which areN-substituted by, for example, one or two identical or differentradicals selected from the group consisting of alkyl, alkoxy, acyl andaryl; preferably monoalkylamino, dialkylamino, acylamino, arylamino,N-alkyl-N-arylamino and N-heterocycles. Preferred in this context arealkyl radicals having 1 to 4 carbon atoms. By preference, aryl is phenylor substituted phenyl. By preference, substituted aryl is substitutedphenyl. The definition given further below applies to acyl, preferably(C₁-C₄)-alkanoyl. This also applies analogously to substitutedhydroxylamino or hydrazino.

[0110] By preference, optionally substituted phenyl is phenyl which isunsubstituted or mono- or polysubstituted, preferably up totrisubstituted, in the case of halogen such as Cl and F also up topentasubstituted, by identical or different radicals selected from thegroup consisting of halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy and nitro, for example o-, m- andp-tolyl, dimethylphenyls, 2-, 3- and 4-chlorophenyl, 2-, 3- and4-trifluoro- and -trichlorophenyl, 2,4-, 3,5-, 2,5- and2,3-dichlorophenyl, o-, m- and p-methoxyphenyl.

[0111] An acyl radical is the radical of an organic acid having bypreference up to 6 carbon atoms, for example the radical of a carboxylicacid and radicals of acids derived therefrom, such as thiocarboxylicacid, optionally N-substituted iminocarboxylic acids, or the radical ofcarbonic monoesters, optionally N-substituted carbamic acids, sulfonicacids, sulfinic acids, phosphonic acids, phosphinic acids. Acyl is, forexample, formyl, alkylcarbonyl such as (C₁-C₄-alkyl)carbonyl,phenylcarbonyl, it being possible for the phenyl ring to be substituted,for example as indicated above for phenyl, or alkyloxycarbonyl,phenyloxycarbonyl, benzyloxycarbonyl, alkylsulfonyl, alkylsulfinyl orN-alkyl-1-iminoalkyl.

[0112] All stereoisomers which show the same topological linkage of theatoms, and their mixtures, also fall under the formulae (I) to (VIII).Such compounds contain one or more asymmetric carbon atoms or elsedouble bonds which are not indicated specifically in the generalformulae. The stereoisomers which are possible which are defined bytheir specific spatial form, such as enantiomers, diastereomers, Z- andE-isomers, can be obtained from mixtures of the stereoisomers bycustomary methods or else be prepared by stereoselective reactions incombination with the use of stereochemically pure starting materials.

[0113] Herbicidally active substances which are suitable in accordancewith the invention are those compounds of the formula (I) which, ontheir own, cannot be used, or not optimally used, in crops of usefulplants such as cereal crops, rice or corn because they are too harmfulto the crop plants.

[0114] Herbicides of the formula (I) are known, for example, from WO-A00/21924 and WO-A 01/7422.

[0115] The cited publications contain extensive data on preparationprocesses and starting materials. These publications are referred toexclusively and are considered by such reference to be part of thisdescription.

[0116] The compounds of the formula (II) are known, for example, fromEP-A-0 333 131 (ZA-89/1960), EP-A-0 269 806 (U.S. Pat. No. 4,891,057),EP-A-0 346 620 (AU-A-89/34951), EP-A-0 174 562, EP-A-0 346 620(WO-A-91/08 202), WO-A-91/07 874 or WO-A 95/07 897 (ZA 94/7120) and theliterature cited therein or can be prepared by or analogously to theprocesses described therein. The compounds of the formula (III) areknown from EP-A-0 086 750, EP-A-0 94349 (U.S. Pat. No. 4,902,340),EP-A-0 191736 (U.S. Pat. No. 4,881,966) and EP-A-0 492 366 and theliterature cited therein or can be prepared by or analogously to theprocesses described therein. Furthermore, some compounds are describedin EP-A-0 582 198. The compounds of the formula (II) are known from alarge number of patent applications, for example U.S. Pat. No. 4,021,224and U.S. Pat. No. 4,021,229. Moreover, compounds of group (b) are knownfrom CN-A-87/102 789, EP-A-0 365 484 and from “The Pesticide Manual”,The British Crop Protection Council and the Royal Society of Chemistry,11th edition, Farnham 1997. The compounds of group (c) are described inWO-A-97/45016, those of group (d) in German Patent Application 197 42951.3 and those of group (e) in WO-A 98/13 361.

[0117] The publications cited contain detailed information onpreparation processes and starting materials. These publications arereferred to explicitly and are considered by such reference to be partof this description.

[0118] For the purpose of the present specification, the terms“herbicidal compositions” and “herbicide/safener combinations” are to beunderstood as being synonymous.

[0119] Preference is given to herbicidal compositions comprisingcompounds of the formula (I) wherein the symbols and indices have thefollowing definitions:

[0120] R¹ is nitro, cyano, chlorine, fluorine, methyl, trifluoromethyl,methylsulfonyl or ethylsulfonyl;

[0121] R² is pentafluoroethoxymethyl, 2,2-difluoroethoxymethyl,2,2,2-trifluoroethoxymethyl, 2,2,3,3-tetrafluoropropoxymethyl,cyclopentyloxymethyl, cyclohexyloxymethyl, cyclopropyloxy,tetrahydrofuran-2-ylmethoxymethyl, methoxyethoxyethoxymethyl, or4,5-dihydroisoxazol-3-yl substituted by a radical from the groupconsisting of cyanomethyl, ethoxymethyl and methoxymethyl;

[0122] R³ is OR⁵;

[0123] R⁵ is hydrogen;

[0124] a is 2;

[0125] b is 0, and in which the two radicals R¹ are in positions 2 and 4of the phenyl ring.

[0126] Preferred herbicidal compositions are those which comprisesafeners of the formula (II) and/or (III) wherein the symbols andindices have the following definitions:

[0127] R²⁴ is hydrogen, (C₁-C₁₈)-alkyl, (C₃-C₁₂)-cycloalkyl,(C₂-C₈)-alkenyl and (C₂-C₁₈)-alkynyl, where the carbon-containing groupscan be substituted by one or more, preferably up to three, radicals R⁵⁰;

[0128] R⁵⁰ is identical or different and is halogen, hydroxyl,(C₁-C₈)-alkoxy, (C₁-C₈)-alkylthio, (C₂-C₈)-alkenylthio,(C₂-C₈)-alkynylthio, (C₂-C₈)-alkenyloxy, (C₂-C₈)-alkynyloxy,(C₃-C₇)-cycloalkyl, (C₃-C₇)-cycloalkoxy, cyano, mono- anddi-(C₁-C₄)-alkylamino, carboxyl, (C₁-C₈)-alkoxycarbonyl,(C₂-C₈)-alkenyloxycarbonyl, (C₁-C₈)-alkylthiocarbonyl,(C₂-C₈)-alkynyloxycarbonyl, (C₁-C₈)-alkylcarbonyl,(C₂-C₈)-alkenylcarbonyl, (C₂-C₈)-alkynylcarbonyl,1-(hydroxyimino)-(C₁-C₆)-alkyl, 1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl,1-[(C₁-C₄)-alkoxyimino]-(C₁-C₆)-alkyl, (C₁-C₈)-alkylcarbonylamino,(C₂-C₈)-alkenylcarbonylamino, (C₂-C₈)-alkynylcarbonylamino,aminocarbonyl, (C₁-C₈)-alkylaminocarbonyl,di-(C₁-C₆)-alkylaminocarbonyl, (C₂-C₆)-alkenylaminocarbonyl,(C₂-C₆)-alkynylaminocarbonyl, (C₁-C₈)-alkoxycarbonylamino,(C₁-C₈)-alkylaminocarbonylamino, (C₁-C₆)-alkylcarbonyloxy which isunsubstituted or substituted by R⁵¹, or is (C₂-C₆)-alkenylcarbonyloxy,(C₂-C₆)-alkynylcarbonyloxy, (C₁-C₈)-alkylsulfonyl, phenyl,phenyl-(C₁-C₆)-alkoxy, phenyl-(C₁-C₆)-alkoxycarbonyl, phenoxy,phenoxy-(C₁-C₆)-alkoxy, phenoxy-(C₁-C₆)-alkoxycarbonyl,phenylcarbonyloxy, phenylcarbonylamino,phenyl-(C₁-C₆)-alkylcarbonylamino, the last-mentioned 9 radicals on thephenyl ring being unsubstituted or mono- or polysubstituted, preferablyup to trisubstituted, by radicals R⁵²; SiR′₃, —OSiR′₃,R′₃Si-(C₁-C₈)-alkoxy, —CO—O—NR′₂, —O—N═CR₁₂, —N═CR′₂, —O—N—R′₂, —NR′₂,CH(OR′)₂, O—(CH₂)_(m)-CH(OR′)₂, —CR′″(OR′)₂, —O—(CH₂)_(m)CR′″(OR″)₂ orby R″O—CHR′″CHCOR″—(C₁-C₆)-alkoxy,

[0129] R⁵¹ is identical or different and is halogen, nitro,(C₁-C₄)-alkoxy and phenyl which is unsubstituted or substituted by oneor more, preferably up to three, radicals R⁵¹;

[0130] R⁵² is identical or different and is halogen, (C₁-C₄)-alkyl,(C₁-C₄)-alkoxy, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy or nitro;

[0131] R′ is identical or different and is hydrogen, (C₁-C₄)-alkyl,phenyl which is unsubstituted or substituted by one or more, preferablyup to three, radicals R⁵², or two radicals R′ together form a(C₂-C₆)-alkanediyl chain;

[0132] R″ is identical or different and is (C₁-C₄)-alkyl, or tworadicals R″ together form a (C₂-C₆)-alkanediyl chain;

[0133] R′″ is hydrogen or (C₁-C₄)-alkyl;

[0134] w is 0, 1,2,3,4, 5 or 6.

[0135] Especially preferred are herbicidal compositions which comprisesafeners of the formula (II) and/or (III) wherein the symbols andindices have the following definitions:

[0136] R²⁴ is hydrogen, (C₁-C₈)-alkyl or (C₃-C₇)-cycloalkyl, the abovecarbon-containing radicals being unsubstituted or mono- orpolysubstituted by halogen or mono- or disubstituted, by preferencemonosubstituted, by radicals R⁵⁰,

[0137] R⁵⁰ is identical or different and is hydroxyl, (C₁-C₄)-alkoxy,carboxyl, (C₁-C₄)-alkoxycarbonyl, (C₂-C₆)-alkenyloxycarbonyl,(C₂-C₆)-alkynyloxycarbonyl, 1-(hydroxyimino)-(C₁-C₄)-alkyl,1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl and1-[(C₁-C4)-alkoxyimino]-(C₁-C₄)-alkyl; —SiR′₃, —O—N═CR′₂, —N═CR′₂, —NR′₂and —ONR′₂ where R′ is identical or different and is hydrogen,(C₁-C₄)-alkyl or, as a pair, a (C₄-C₅)-alkanediyl chain,

[0138] R²⁷, R²⁸, R²⁹ are identical or different and are hydrogen,(C₁-C₈)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₇)-cycloalkyl or phenyl which isunsubstituted or substituted by one or more radicals selected from thegroup consisting of halogen, cyano, nitro, amino, mono- anddi-[(C₁-C₄)-alkyl]amino, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio and (C₁-C₄)—alkylsulfonyl;

[0139] R¹⁷, R¹⁹ are identical or different and are hydrogen, halogen,methyl, ethyl, methoxy, ethoxy, (C₁ or C₂)-haloalkyl, by preferencehydrogen, halogen or (C₁ or C₂)-haloalkyl.

[0140] Especially preferred are herbicidal compositions comprisingsafeners of the formula (II) in which the symbols and indices have thefollowing definitions:

[0141] R¹⁷ is hydrogen, halogen, nitro or (C₁-C₄)-haloalkyl;

[0142] n′ is 1, 2 or 3;

[0143] R¹⁸ is a radical of the formula OR²⁴;

[0144] R²⁴ is hydrogen, (C₁-C₈)-alkyl or (C₃-C₇)-cycloalkyl, where theabove carbon-containing radicals are unsubstituted or mono- orpolysubstituted, by preference up to trisubstituted, by identical ordifferent halogen radicals or up to disubstituted, by preferencemonosubstituted, by identical or different radicals selected from thegroup consisting of hydroxyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxycarbonyl,(C₂-C₆)-alkenyloxycarbonyl, (C₂-C₆)-alkynyloxycarbonyl,1-(hydroxyimino)-(C₁-C₄)-alkyl, 1-[(C₁-C₄)-alkylimino]-(C_(—C)4)-alkyl,1-[(C₁-C₄)-alkoxyimino]-(C₁-C₄)-alkyl and radicals of the formulae—SiR′₃, —O—N═R′₂, —N═CR′₂, —NR′₂ and —O—NR′₂, where the radicals R′ inthe above-mentioned formulae are identical or different and arehydrogen, (C₁-C₄)-alkyl or, as a pair, are (C₄ or C₅)-alkanediyl;

[0145] R²⁷, R²⁸, R²⁹ are identical or different and are hydrogen,(C₁-C₈)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₇)-cycloalkyl or phenyl which isunsubstituted or substituted by one or more of the radicals selectedfrom the group consisting of halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,nitro, (C₁-C₄)-haloalkyl and (C₁-C₄)-haloalkoxy.

[0146] Also especially preferred are herbicidal compositions comprisingsafeners of the formula (III) wherein the symbols and indices have thefollowing definitions:

[0147] R¹⁹ is hydrogen, halogen or (C₁-C₄)-haloalkyl;

[0148] n′ is 1, 2 or 3, where (R¹⁹)_(n′) is by preference 5-Cl;

[0149] R²⁰ is a radical of the formula OR²⁴;

[0150] T is CH₂and

[0151] R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl or(C₁-C₄)-alkoxy-(C₁-C₄)-alkyl, by preference (C₁-C₈)-alkyl.

[0152] Especially preferred are herbicidal compositions comprisingsafeners of the formula (II) wherein the symbols and indices have thefollowing definitions:

[0153] W is (W1);

[0154] R¹⁷ is hydrogen, halogen or (C₁-C₂)-haloalkyl;

[0155] n′ is 1, 2 or 3, where (R¹⁷)_(n) is by preference 2,4-Cl₂;

[0156] R¹⁸ is a radical of the formula OR²⁴;

[0157] R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,(C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkylor tri-(C₁-C₂)-alkylsilyl, by preference (C₁-C₄)-alkyl;

[0158] R²⁷ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl or(C₃-C₇)-cycloalkyl, by preference hydrogen or (C₁-C₄)-alkyl, and

[0159] R²⁶ is hydrogen or (C₁-C₄)-alkyl.

[0160] Also especially preferred are herbicidal compositions comprisingsafeners of the formula (II) wherein the symbols and indices have thefollowing definitions:

[0161] W is (W2);

[0162] R¹⁷ is hydrogen, halogen or (C₁-C₂)-haloalkyl;

[0163] n′ is 1, 2 or 3, where (R¹⁷)_(n′) is by preference 2,4-Cl₂;

[0164] R¹⁸ is a radical of the formula OR²⁴;

[0165] R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,(C₁-C₄)-hydroxyalkyl, (C₃-C₇)-cycloalkyl, (C₁-C₄-alkoxy)-C₁-C₄-alkyl ortri-(C₁-C₂)-alkyl-silyl, by preference (C₁-C₄)-alkyl, and

[0166] R²⁷ is hydrogen, (C₁-C₈)-alkyl, (C₁-C₄)-haloalkyl,(C₃-C₇)-cycloalkyl or phenyl, by preference hydrogen or (C₁-C₄)-alkyl.

[0167] Also especially preferred are herbicidal compositions comprisingsafeners of the formula (II) wherein the symbols and indices have thefollowing definitions:

[0168] W is (W3);

[0169] R¹⁷ is hydrogen, halogen or (C₁-C₂)-haloalkyl;

[0170] n′ is 1, 2 or 3, where (R¹⁷)_(n) is by preference 2,4-Cl₂;

[0171] R¹⁸ is a radical of the formula OR²⁴;

[0172] R²⁴ is hydrogen, (C₁-C₈)-alkyl, (C₃-C₇)-cycloalkyl, by preference(C₁-C₄)-alkyl, and

[0173] R²⁸ is (C₁-C₈)-alkyl or (C₁-C₄)-haloalkyl, by preferenceC₁-haloalkyl.

[0174] Also especially preferred are herbicidal compositions comprisingsafeners of the formula (II) wherein the symbols and indices have thefollowing definitions:

[0175] W is (W4);

[0176] R¹⁷ is hydrogen, halogen, nitro, (C₁-C₄)-alkyl,(C₁-C₂)-haloalkyl, by preference CF₃;

[0177] n′ is 1, 2 or 3;

[0178] m′ is 0 or 1;

[0179] R¹⁸ is a radical of the formula OR²⁴;

[0180] R²⁴ is hydrogen, (C₁-C₄)-alkyl, carboxy-(C₁-C₄)-alkyl,(C₁-C₄)-alkoxycarbonyl-(C₁₁-C₄)-alkyl, by preference(C₁-C₄)-alkoxy-CO—CH₂—, (C₁-C₄)-alkoxy-CO—C(CH₃)(H)—, HO—CO—CH₂— orHO—CO—C(CH₃)(H)—, and

[0181] R²⁹ is hydrogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₃-C₇)-cycloalkyl or phenyl which is unsubstituted or substituted byone or more of the radicals selected from the group consisting ofhalogen, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, nitro, cyano and(C₁-C₄)-alkoxy.

[0182] The following groups of compounds are especially suitable for useas safeners for the herbicidally active substances of the formula (I):

[0183] a) Compounds of the dichlorophenylpyrazoline-3-carboxylic acidtype (i.e. of the formula (II) where W=W1 and (R¹⁷)_(n′)=2,4-Cl₂), bypreference compounds such as ethyl1-(2,4-dichlorophenyl)-5-(ethoxycarbonyl)-5-methyl-2-pyrazoline-3-carboxylate(II-1), and related compounds as they are described in WO-A 91/07874;

[0184] b) dichlorophenylpyrazolecarboxylic acid derivatives (i.e. of theformula (II) where W=(W2) and (R¹⁷)_(n′)=2,4-Cl₂), by preferencecompounds such as ethyl1-(2,4-dichlorophenyl)-5-methylpyrazole-3-carboxylate (11-2), ethyl1-(2,4-dichlorophenyl)-5-isopropylpyrazole-3-carboxylate (II-3), ethyl1-(2,4-dichlorophenyl)-5-(1,1-dimethylethyl)pyrazole-3-carboxylate(II-4), ethyl 1-(2,4-dichlorophenyl)-5-phenylpyrazole-3-carboxylate(II-5) and related compounds as they are described in EP-A-0 333 131 andEP-A-0 269 806.

[0185] c) Compounds of the triazolecarboxylic acid type (i.e. of theformula (II) where W=(W3) and (R¹⁷)_(n′)=2,4-Cl₂), by preferencecompounds such as fenchlorazol, i.e. ethyl1-(2,4-dichlorophenyl)-5-trichloromethyl-(1H)-1,2,4-triazole-3-carboxylate(II-6), and related compounds (see EP-A-0 174 562 and EP-A-0 346 620);

[0186] d) compounds of the 5-benzyl- or5-phenyl-2-isoxazoline-3-carboxylic acid type or the5,5-diphenyl-2-isoxazoline-3-carboxylic acid type (where W=(W4)), bypreference compounds such as ethyl5-(2,4-dichlorobenzyl)-2-isoxazoline-3-carboxylate (II-7) or ethyl5-phenyl-2-isoxazoline-3-carboxylate (II-8) and related compounds asthey are described in WO-A-91/08202, or ethyl5,5-diphenyl-2-isoxazoline-3-carboxylate (II-9) or n-propyl5,5-diphenyl-2-isoxazoline-3-carboxylate (II-10) or ethyl5-(4-fluorophenyl)-5-phenyl-2-isoxazoline-3-carboxylate (II-11), as theyare described in WO-A-95/07897.

[0187] e) Compounds of the 8-quinolinoxyacetic acid type, for examplethose of the formula (III) where (R¹⁹)_(n′)=5-Cl or hydrogen, R²⁰=OR²⁴and T=CH₂, by preference the compounds

[0188] 1-methylhexyl (5-chloro-8-quinolinoxy)acetate (III-1,cloquintocet-mexyl),

[0189] 1,3-dimethylbut-1-yl (5-chloro-8-quinolinoxy)acetate (III-2),

[0190] 4-allyloxybutyl (5-chloro-8-quinolinoxy)acetate (III-3),

[0191] 1-allyloxyprop-2-yl (5-chloro-8-quinolinoxy)acetate (III-4),

[0192] ethyl (5-chloro-8-quinolinoxy)acetate (III-5),

[0193] methyl (5-chloro-8-quinolinoxy)acetate (III-6),

[0194] allyl (5-chloro-8-quinolinoxy)acetate (III-7),

[0195] 2-(2-propylideniminoxy)-1-ethyl (5-chloro-8-quinolinoxy)acetate(III-8),

[0196] 2-oxoprop-1-yl (5-chloro-8-quinolinoxy)acetate (III-9)

[0197] and related compounds as they are described in EP-A-0 860 750,EP-A-0 094 349 and EP-A-0 191 736 or EP-A-0 492 366.

[0198] f) Compounds of the (5-chloro-8-quinolinoxy)malonic acid type,i.e. of the formula (III) where (R¹⁷)_(n′)=5-Cl, R²⁰=OR²⁴,T=CH(COO-alkyl)-, by preference the compounds diethyl(5-chloro-8-quinolinoxy)malonate, diallyl(5-chloro-8-quinolinoxy)malonate, methyl ethyl(5-chloro-8-quinolinoxy)malonate and related compounds as they aredescribed in EP-A-0 582 198.

[0199] g) Compounds of the dichloroacetamide type, i.e. of the formula(IV), by preference:

[0200] N,N-diallyl-2,2-dichloroacetamide (dichlormid, from U.S. Pat. No.4,137,070),

[0201] 4-dichloroacetyl-3,4-dihydro-3-methyl-2H-1,4-benzoxazine(benoxacor, from EP 0 149 974),

[0202] N1,N2-diallyl-N-2-dichloroacetylglycinamide (DKA-24, from HU2143821),

[0203] 4-dichloroacetyl-1-oxa-4-azaspiro[4,5]decane (AD-67),

[0204] 2,2-dichloro-N-(1,3-dioxolan-2-ylmethyl)-N-(2-propenyl)acetamide(PPG-1292),

[0205] 3-dichloroacetyl-2,2,5-trimethyloxazolidine,

[0206] 3-dichloroacetyl-2,2-dimethyl-5-phenyloxazolidine,

[0207] 3-dichloroacetyl-2,2-dimethyl-5-(2-thienyl)oxazolidine,

[0208] 3-dichloroacetyl-5-(2-furanyl)-2,2-dimethyloxazolidine(furilazole, MON 13900),

[0209]1-dichloroacetylhexahydro-3,3,8a-trimethylpyrrolo[1,2-a]pyrimidin-6(2H)-one (dicyclonon, BAS 145138),

[0210] h) compounds of group B(b), by preference

[0211] 1,8-naphthalic anhydride,

[0212] methyl diphenylmethoxyacetate,

[0213] cyanomethoxyimino(phenyl)acetonitrile (cyometrinil),

[0214] 1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil),

[0215] 4′-chloro-2,2,2-trifluoroacetophenone O-1,3-dioxolan-2-ylmethyloxime (fluxofenim),

[0216] 4,6-dichloro-2-phenylpyrimidine (fenclorim),

[0217] benzyl 2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate(flurazole),

[0218] 2-dichloromethyl-2-methyl-1,3-dioxolane (MG-191),

[0219] N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),

[0220] 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,

[0221] 1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,

[0222] 1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,

[0223] 1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea,

[0224] (2,4-dichlorophenoxy)acetic acid (2,4-D),

[0225] (4-chlorophenoxy)acetic acid,

[0226] (R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),

[0227] 4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),

[0228] (4-chloro-o-tolyloxy)acetic acid (MCPA),

[0229] 4-(4-chloro-o-tolyloxy)butyric acid,

[0230] 4-(4-chlorophenoxy)butyric acid,

[0231] 3,6-dichloro-2-methoxybenzoic acid (dicamba),

[0232] 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate(lactidichlor),

[0233] and their salts and esters, by preference (C₁-C₈).

[0234] Further preferred safeners are compounds of the formula (V) orsalts thereof in which

[0235] R³⁰ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl, where each ofthe last-mentioned 2 radicals is unsubstituted or substituted by one ormore substituents selected from the group consisting of halogen,(C₁-C₄)-alkoxy, halo-(C₁-C₆)-alkoxy and (C₁-C₄)-alkylthio and, in thecase of cyclic radicals, also (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl,

[0236] R³¹ is hydrogen;

[0237] R³² is halogen, halo-(C₁-C₄)-alkyl, halo-(C₁-C₄)-alkoxy,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl, by preference halogen,(C₁-C₄)-haloalkyl such as trifluoromethyl, (C₁-C₄)-alkoxy,halo-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylsulfonyl,

[0238] R³³ is hydrogen;

[0239] R³⁴ is halogen, (C₁-C₄)-alkyl, halo-(C₁-C₄)-alkyl,halo-(C₁-C₄)-alkoxy, (C₃-C₆)-cycloalkyl, phenyl, (C₁-C₄)-alkoxy, cyano,(C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl, by preference halogen,(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl such as trifluoromethyl,halo-(C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy or (C₁-C₄)-alkylthio,

[0240] n is 0, 1 or 2and

[0241] m is 1 or 2.

[0242] Also preferred are safeners of the formula (VI) in which

[0243] X³ is CH;

[0244] R³⁵ is hydrogen, (C₁-C₆)-alkyl, (C₃-C₆)-cycloalkyl,(C₂-C₆)-alkenyl, (C₅-C₆)-cycloalkenyl, phenyl or 3- to 6-memberedheterocyclyl having up to three heteroatoms selected from the groupconsisting of nitrogen, oxygen and sulfur, the six last-mentionedradicals optionally being substituted by one or more identical ordifferent substituents selected from the group consisting of halogen,(C₁-C₆)-alkoxy, (C₁-C₆)-haloalkoxy, (C₁-C₂)-alkylsulfinyl,(C₁-C₂)-alkylsulfonyl, (C₃-C₆)-cycloalkyl, (C₁-C₄)-alkoxycarbonyl,(C₁-C₄)-alkylcarbonyl and phenyl and in the case of cyclic radicals,also (C₁-C₄)-alkyl and (C₁-C₄)-haloalkyl;

[0245] R³⁶ is hydrogen, (C₁-C₆)-alkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl,the three last-mentioned radicals optionally being substituted by one ormore identical or different substituents selected from the groupconsisting of halogen, hydroxyl, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and(C₁-C₄)-alkylthio;

[0246] R³⁷ is halogen, (C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy, nitro,(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl;

[0247] R³⁸ is hydrogen;

[0248] R³⁹ is halogen, nitro, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₁-C₄)-haloalkoxy, (C₃-C₆)-cycloalkyl, phenyl, (C₁-C₄)-alkoxy, cyano,(C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl, (C₁-C₄)-alkylsulfonyl,(C₁-C₄)-alkoxycarbonyl or (C₁-C₄)-alkylcarbonyl;

[0249] r is 0, 1 or 2and

[0250] q is 1 or 2.

[0251] Further particularly preferred safeners are compounds of theformula (VII), in which

[0252] R⁴⁰ is trifluoromethyl,

[0253] R⁴¹ is hydrogen, and

[0254] R⁴² is hydrogen, methyl or ethyl.

[0255] The compounds cited here as safeners (antidotes) reduce orprevent phytotoxic effects which may occur when using the herbicidallyactive substances of the formula (I) in crops of useful plants withoutsubstantially affecting the activity of these herbicidally activesubstances against weed plants. This allows the field of application ofconventional crop protection products to be widened quite considerablyand to be extended to, for example, crops such as wheat, barley, corn,and sugar cane in which use of the herbicides was hitherto impossible,or of only limited possibility, that is to say at low rates and with arestricted spectrum.

[0256] The herbicidally active substances and the abovementionedsafeners can be applied together (as a readymix or by the tank mixmethod) or in succession in any desired sequence. The weight ratio ofsafener to herbicidally active substance may vary within wide limits andis preferably within the range from 1:100 to 100:1, in particular from1:10 to 10:1. The optimum amounts of herbicidally active substance andsafener in each case depend on the type of the herbicidally activesubstance used or on the safener used and on the species of the plantstand to be treated and can be determined in each individual case bysimple, routine preliminary experiments.

[0257] Main fields of application for the combinations according to theinvention are, in particular, corn, sugar cane and cereal crops forexample wheat, rye, barley, oats, rice, sorghum, but also cotton andsoybeans, preferably sugar cane, cereals, rice and corn.

[0258] Depending on their properties, the safeners employed inaccordance with the invention can be used for pretreating the seeds of acrop plant (seed dressing), or be incorporated into the seed furrowsprior to sowing or applied together with the herbicide before or afterplant emergence. The preemergence treatment includes both the treatmentof the area under cultivation prior to sowing and the treatment of theareas under cultivation where the seeds have been planted but the plantshave not yet emerged. Joint application with the herbicide is preferred.To this end, tank mixes or readymixes can be employed.

[0259] The application rates of safener required may vary within widelimits depending on the indication and the herbicidally active substanceused and are generally in the range of from 0.001 to 5 kg, preferably0.005 to 0.5 kg, of active substance per hectare.

[0260] The present invention therefore also provides a method ofprotecting crop plants from phytotoxic side effects of herbicides of theformula (I), which comprises applying an antidote-active amount of acompound of the formula (II), (III), (IV), (V), (VI), (VII) and/or fromgroup (b) to the plants, the seeds of the plants or the area undercultivation, before, after or simultaneously with the herbicidallyactive substance A of the formula (I).

[0261] The herbicide/safener combination according to the invention mayalso be employed for controlling weed plants in crops of geneticallyengineered plants which are either known or still to be developed. As arule, the transgenic plants are distinguished by particular,advantageous properties, for example by resistances to certain cropprotection agents, resistances to plant diseases or pathogens causingplant diseases such as particular insects or microorganisms such asfungi, bacteria or viruses. Other particular properties relate, forexample, to the harvested material in terms of quantity, quality,storing properties, composition and specific constituents. Thus,transgenic plants are known which have an increased starch content or analtered starch quality, or those where the harvested material has adifferent fatty acid composition.

[0262] The use of the combinations according to the invention ispreferred in economically important transgenic crops of useful plantsand ornamentals, for example cereals such as wheat, barley, rye, oats,millet, rice, cassaya and corn or else crops of sugar beet, cotton,soya, oilseed rape, potatoes, tomatoes, peas and other types ofvegetables.

[0263] When the combinations according to the invention are employed intransgenic crops, effects on weed plants to be observed in other cropsare frequently accompanied by effects which are specific for applicationin the transgenic crop in question, for example an altered orspecifically widened weed spectrum which can be controlled, alteredapplication rates which may be used, preferably good compatibility withthe herbicides to which the transgenic crop is resistant, and alteredgrowth and yield of the transgenic crop plants.

[0264] The invention therefore also provides for the use of thecombination according to the invention for controlling weed plants intransgenic crop plants.

[0265] The safeners of the formulae (III)-(VII) and of group (b) andtheir combinations with one or more of the abovementioned herbicidallyactive substances of the formula (I) can be formulated in various ways,depending on the biological and/or chemico-physical parametersspecified. Examples of suitable formulations which are possible are:wettable powders (WP), emulsifiable concentrates (EC), water-solublepowders (SP), water-soluble concentrates (SL), concentrated emulsions(BW) such as oil-in-water and water-in-oil emulsions, sprayablesolutions or emulsions, capsule suspensions (CS), oil- or water-baseddispersions (SC), suspoemulsions, suspension concentrates, dusts (DP),oil-miscible solutions (OL), seed dressing products, granules (GR) inthe form of microgranules, spray granules, coated granules andadsorption granules, granules for soil application or broadcasting,water-soluble granules (SG), water-dispersible granules (WG), ULVformulations, microcapsules and waxes.

[0266] These individual formulation types are known in principle anddescribed, for example, in: Winnacker-Küchler, “Chemische Technologie”[Chemical Engineering], Volume 7, C. Hauser Verlag Munich, 4^(th)Edition 1986; Wade van Valkenburg, “Pesticide Formulations”, MarcelDekker N.Y., 1973; K. Martens, “Spray Drying Handbook”, 3^(rd) Ed. 1979,G. Goodwin Ltd. London.

[0267] The formulation auxiliaries which may be required, such as inertmaterials, surfactants, solvents and other additives are also known anddescribed, for example, in: Watkins, “Handbook of Insecticide DustDiluents and Carriers”, 2^(nd) Ed., Darland Books, Caldwell N.J., H.v.Olphen, “Introduction to Clay Colloid Chemistry”, 2^(nd) Ed., J. Wiley &Sons, N.Y.; C. Marsden, “Solvents Guide”, 2^(nd) Ed., Interscience, N.Y.1963; McCutcheon's “Detergents and Emulsifiers Annual”, MC Publ. Corp.,Ridgewood N.J.; Sisley and Wood, “Encyclopedia of Surface ActiveAgents”, Chem. Publ. Co. Inc., N.Y. 1964; Schönfeldt,“Grenzflächenaktive Äthylenoxidaddukte” [Surface-active Ethylene OxideAdducts], Wiss. Verlagsgesell., Stuttgart 1976; Winnacker-Küchler,“Chemische Technologie” [Chemical Engineering], Volume 7, C. HauserVerlag Munich, 4th Edition 1986.

[0268] Based on these formulations, it is also possible to preparecombinations with other substances which act as crop protection agents,such as insecticides, acaricides, herbicides, fungicides, and also withsafeners, fertilizers and/or growth regulators, for example in the formof a readymix or as a tank mix.

[0269] Wettable powders are preparations which are uniformly dispersiblein water and which, besides the active substance, also comprise ionicand/or nonionic surfactants (wetting agents, dispersants), for examplepolyoxyethylated alkylphenols, polyoxyethylated fatty alcohols,polyoxyethylated fatty amines, fatty alcohol polyglycol ether sulfates,alkanesulfonates, alkylbenzenesulfonates, sodium lignosulfonate, sodium2,2′-dinaphthylmethane-6,6′-disulfonate, sodiumdibutylnaphthalenesulfonate, or else sodium oleoylmethyltaurinate, inaddition to a diluent or inert substance. To prepare the wettablepowders, the herbicidally active substances are ground finely, forexample in customary apparatus such as hammer mills, blower mills andair-jet mills, and they are simultaneously or subsequently mixed withthe formulation auxiliaries.

[0270] Emulsifiable concentrates are prepared, for example, bydissolving the active substance in an organic solvent such as butanol,cyclohexanone, DMF, or else higher-boiling hydrocarbons such assaturated or unsaturated aliphatics or alicycles, aromatics or mixturesof the organic solvents with the addition of one or more ionic and/ornonionic surfactants (emulsifiers). Examples of substances which can beused as emulsifiers are: calcium alkylarylsulfonates such as calciumdodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acidpolyglycol esters, alkylarylpolyglycol ethers, fatty alcohol polyglycolethers, propylene oxide/ethylene oxide condensates, alkyl polyethers,sorbitan esters, such as sorbitan fatty acid esters or polyoxyethylenesorbitan esters such as polyoxyethylene sorbitan fatty acid esters.Dusts are generally obtained by grinding the active substance withfinely divided solid substances, for example talc, natural clays such askaolin, bentonite and pyrophyllite, or diatomaceous earth.

[0271] Suspension concentrates can be water- or oil-based. They can beprepared, for example, by wet-grinding using commercially available beadmills with or without addition of surfactants, for example those whichhave already been mentioned above in the case of the other formulationtypes.

[0272] Emulsions, for example oil-in-water emulsions (EW), can beprepared, for example, by means of stirrers, colloid mills and/or staticmixers using aqueous organic solvents in the presence or absence ofsurfactants which have already been mentioned above, for example, in thecase of the other formulation types.

[0273] Granules can be prepared either by spraying the active substanceonto adsorptive, granulated inert material or by applying activesubstance concentrates to the surface of carriers such as sand,kaolinites or granulated inert material with the aid of binders, forexample polyvinyl alcohol, sodium polyacrylate or else mineral oils.Suitable active substances can also be granulated in the manner which isconventional for the preparation of fertilizer granules, if desired as amixture with fertilizers. As a rule, water-dispersible granules areprepared by the customary processes such as spray-drying, fluidized-bedgranulation, disk granulation, mixing with high-speed mixers andextrusion without solid inert material.

[0274] For the preparation of disk, fluidized-bed, extruder and spraygranules see, for example, “Spray-Drying Handbook” 3^(rd) ed. 1979, G.Goodwin Ltd., London; J. E. Browning, “Agglomeration”, Chemical andEngineering 1967, pages 147 et seq.; “Perry's Chemical Engineer'sHandbook”, 5^(th) Ed., McGraw-Hill, New York 1973, p. 8-57.

[0275] For further details on the formulation of crop protectionproducts see, for example, G. C. Klingman, “Weed Control as a Science”,John Wiley and Sons, Inc., New York, 1961, pages 81-96 and J. D. Freyer,S. A. Evans, “Weed Control Handbook”, 5^(th) Ed., Blackwell ScientificPublications, Oxford, 1968, pages 101-103.

[0276] As a rule, the agrochemical formulations comprise 0.1 to 99% byweight, in particular 0.1 to 95% by weight, of active substances of theformulae (II)-(VII) and/or (b) or of the herbicide/antidote mixture ofactive substances (I) and (II)-(VII) and/or (b) and 1 to 99.9% byweight, in particular 5 to 99.8% by weight, of a solid or liquidadditive and 0 to 25% by weight, in particular 0.1 to 25% by weight, ofa surfactant.

[0277] In wettable powders, the active substance concentration is, forexample, approximately 10 to 90% by weight, the remainder to 100% byweight being composed of customary formulation components. In the caseof emulsifiable concentrates, the active substance concentration isapproximately 1 to 80% by weight. Formulations in the form of dustscomprise approximately 1 to 20% by weight of active substances,sprayable solutions approximately 0.2 to 20% by weight of activesubstances. In the case of granules such as water-dispersible granules,the active substance content depends partly on whether the activecompound is in liquid or solid form. The active substance content of thewater-dispersible granules is, as a rule, between 10 and 90% by weight.

[0278] Besides this, the abovementioned formulations of activesubstances comprise, if appropriate, the adhesives, wetters,dispersants, emulsifiers, penetrants, preservatives, antifreeze agents,solvents, fillers, carriers, colorants, antifoams, evaporationinhibitors and pH and viscosity regulators which are customary in eachcase.

[0279] Co-components which can be used for the mixtures of herbicidesand safeners according to the invention in mixed formulations or in atank mix are, for example, known active substances as they aredescribed, for example, in Weed Research 26, 441-445 (1986), or “ThePesticide Manual”, 10^(th) edition, The British Crop Protection Council,1994, and in the literature cited therein. Herbicides which are knownfrom the literature and which can be combined with the mixturesaccording to the invention are, for example, the following activesubstances (note: either the common names in accordance with theInternational Organization for Standardization (ISO) or the chemicalnames, if appropriate together with the customary code number, of thecompounds are given):

[0280] acetochlor; acifluorfen; aclonifen; AKH 7088, i.e.[[[1-[5-[2-chloro-4-(trifluoromethyl)-phenoxy]-2-nitrophenyl]-2-methoxyethylidene]amino]oxy]aceticacid and its methyl ester; alachlor; alloxydim; ametryn; amidosulfuron;amitrol; AMS, i.e. ammonium sulfamate; anilofos; asulam; atrazin;azafenidine (DPX-R6447), azimsulfuron (DPX-A8947); aziprotryn; barban;BAS 516H, i.e. 5-fluoro-2-phenyl-4H-3,1-benzoxazin-4-one; benazolin;benfluralin; benfuresate; bensulfuron-methyl; bensulide; bentazone;benzofluor; benzoylprop-ethyl; benzthiazuron; bialaphos; bifenox;bispyribac-sodium (KIH-2023), bromacil; bromobutide; bromofenoxim;bromoxynil; bromuron; buminafos; busoxinone; butachlor; butamifos;butenachlor; buthidazole; butralin; butroxydim (ICI-0500), butylate;cafenstrole (CH-900); carbetamide; cafentrazone; CDM, i.e.2-chloro-N,N-di-2-propenylacetamide; CDEC, i.e. 2-chloroallyldiethyldithiocarbamate; chlomethoxyfen; chloramben; chloransulam-methyl(XDE-565), chlorazifop-butyl, chlorbromuron; chlorbufam; chlorfenac;chlorflurecol-methyl; chloridazon; chlorimuron-ethyl; chlornitrofen;chlorotoluron; chloroxuron; chlorpropham; chlorsulfuron;chlorthal-dimethyl; chlorthiamid; cinidon-ethyl, cinmethylin;cinosulfuron; clefoxydim, clethodim; clodinafop and its esterderivatives (for example clodinafop-propargyl); clomazone; clomeprop;cloproxydim; clopyralid; cumyluron (JC 940); cyanazine; cycloate;cyclosulfamuron (AC 014); cycloxydim; cycluron; cyhalofop and its esterderivatives (for example butyl ester, DEH-1 12); cyperquat; cyprazine;cyprazole; 2,4-DB; dalapon; desmedipham; desmetryn; di-allate; dicamba;dichlobenil; dichlorprop; diclofop and its esters such asdiclofop-methyl; diclosulam (XDE-564), diethatyl; difenoxuron;difenzoquat; diflufenican; diflufenzopyr-sodium (SAN-835H), dimefuron;dimethachlor; dimethametryn; dimethenamid (SAN-582H); dimethazone,methyl5-(4,6-dimethylpyrimidin-2-yl-carbamoylsulfamoyl)-1-(2-pyridyl)-pyrazole-4-carboxylate(NC-330); clomazon; dimethipin; dimetrasulfuron, dinitramine; dinoseb;dinoterb; diphenamid; dipropetryn; diquat; dithiopyr; diuron; DNOC;eglinazine-ethyl; EL 177, i.e.5-cyano-1-(1,1-dimethylethyl)-N-methyl-1H-pyrazole-4-carboxamide;endothal; epoprodan (MK-243), EPTC; esprocarb; ethalfluralin;ethametsulfuron-methyl; ethidimuron; ethiozin; ethofumesate; F5231, i.e.N-[2-chloro-4-fluoro-5-[4-(3-fluoropropyl)-4,5-dihydro-5-oxo-1H-tetrazol-1-yl]phenyl]ethanesulfonamide;ethoxyfen and its ester (for example ethyl ester, HN-252);ethoxysulfuron (from EP 342569); etobenzanid (HW 52);3-(4-ethoxy-6-ethyl-1,3,5-triazin-2-yl)-1-(2,3-dihydro-1,1-dioxo-2-methylbenzo[b]thiophene-7-sulfonyl)urea(EP-A 079 683);3-(4-ethyl-6-methoxy-1,3,5-triazin-2-yl)-1-(2,3-dihydro-1,1-dioxo-2-methylbenzo[b]thiophene-7-sulfonyl)urea(EP-A 079 683); fenoprop; fenoxan, fenoxaprop and fenoxaprop-P and theiresters, for example fenoxaprop-P-ethyl and fenoxaprop-ethyl; fenoxydim;fentrazamide (NBA-061); fenuron; flamprop-methyl; flazasulfuron;flufenacet (BAY-FOE-5043), fluazifop and fluazifop-P, florasulam(DE-570) and their esters, for example fluazifop-butyl andfluazifop-P-butyl; fluazolate (Mon-48500), fluchloralin;flucarbazone-sodium; flumetsulam; flumeturon; flumiclorac and its esters(for example pentyl ester, S-23031); flumioxazin (S-482); flumipropyn;flupoxam (KNW-739); fluorodifen; fluoroglycofen-ethyl; flupropacil(UBIC-4243); sodium flupyrsulfuron-methyl (DPX-KE459), fluridone;flurochloridone; fluroxypyr; flurtamone; fluthiacet-methyl (K1H-9201),fomesafen; fosamine; furyloxyfen; glufosinate; glyphosate; halosafen;halosulfuron and its esters (for example methyl ester, NC-319);haloxyfop and its esters; haloxyfop-P (═R-haloxyfop) and its esters;hexazinone; imazamethabenz-methyl; imazamox (AC-299263), imazapyr;imazaquin and salts such as the ammonium salt; imazethamethapyr;imazethapyr; imazosulfuron; iodosulfuron (methyl4-iodo-2-[3-(4-methoxy-6-methyl-1,3,5-triazin-2-yl)ureidosulfonyl]benzoate,sodium salt, WO 92/13845); ioxynil; isocarbamid; isopropalin;isoproturon; isouron; isoxaben; isoxapyrifop; karbutilate; lactofen;lenacil; linuron; MCPA; MCPB; mecoprop; mefenacet; mefluidid;metamitron; metazachlor; methabenzthiazuron; metham; methazole;methoxyphenone; methyldymron; metabenzuron, methyl2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-methanesulfonamidomethylbenzoate(WO 95/10507); methobenzuron; metobromuron; metolachlor; S-metolachlor,metosulam (XRD 511); metoxuron; metribuzin; metsulfuron-methyl; MH;molinate; monalide; monocarbamide dihydrogensulfate; monolinuron;monuron; MT 128, i.e.6-chloro-N-(3-chloro-2-propenyl)-5-methyl-N-phenyl-3-pyridazinamine; MT5950, i.e. N-[3-chloro-4-(1-methylethyl)phenyl]-2-methylpentanamide;N,N-dimethyl-2-[3-(4,6-dimethoxypyrimidin-2-yl)ureidosulfonyl]-4-formylaminobenzamide(WO 95/01344); naproanilide; napropamide; naptalam; NC 310, i.e.4-(2,4-dichlorobenzoyl)-1-methyl-5-benzyloxypyrazole; neburon;nicosulfuron; nipyraclofen; nitralin; nitrofen; nitrofluorfen;norflurazon; orbencarb; oryzalin; oxadiargyl (RP-020630); oxadiazon;oxaziclomefone (MY-100), oxyfluorfen; oxasulfuron (CGA-277476),paraquat; pebulate; pendimethalin; pentoxazone (KPP-314), perfluidone;phenisopham; phenmedipham; picloram; piperophos; piributicarb;pirifenop-butyl; pretilachlor; primisulfuron-methyl;pracarbazone-sodium; procyazine; prodiamine; profluralin;proglinazine-ethyl; prometon; prometryn; propachlor; propanil;propaquizafop and its esters; propazine; propham; propisochlor;propyzamide; prosulfalin; prosulfocarb; prosulfuron (CGA-152005);prynachlor; pyraflufen-ethyl (ET-751), pyrazon; pyrazosulfuron-ethyl;pyrazoxyfen; pyribenzoxim, pyridafol; pyridate; pyriminobac-methyl(KIH-6127), pyrithiobac (KIH-2031); pyroxofop and its esters (forexample propargyl ester); quinclorac; quinmerac; quinofop and its esterderivatives, quizalofop and quizalofop-P and their ester derivatives,for example quizalofop-ethyl; quizalofop-P-tefuryl and -ethyl;renriduron; rimsulfuron (DPX-E 9636); S 275, i.e.2-[4-chloro-2-fluoro-5-(2-propynyloxy)-phenyl]-4,5,6,7-tetrahydro-2H-indazole; secbumeton; sethoxydim; siduron; simazine; simetryn; SN106279, i.e.2-[[7-[2-chloro-4-(trifluoromethyl)phenoxy]-2-naphthalenyl]oxy]propanoicacid and its methyl ester; sulfentrazon (FMC-97285, F-6285); sulfazuron;sulfometuron-methyl; sulfosate (ICI-A0224); sulfosulfuron (MON-37500),TCA; tebutam (GCP-5544); tebuthiuron; tepraloxydim (BAS-620H), terbacil;terbucarb; terbuchlor; terbumeton; terbuthylazine; terbutryn; TFH 450,i.e.N,N-diethyl-3-[(2-ethyl-6-methylphenyl)sulfonyl]-1H-1,2,4-triazole-1-carboxamide;thenylchlor (NSK-850); thiazafluron; thiazopyr (Mon-1 3200); thidiazimin(SN-1 24085); thifensulfuron-methyl; thiobencarb; thiocarbazil;tralkoxydim; tri-allate; triasulfuron; triaziflam (DH-1105);triazofenamide; tribenuron-methyl; triclopyr; tridiphane; trietazine;trifluralin; triflusulfuron and esters (for example methyl ester,DPX-66037); trimeturon; tsitodef; vernolate; WL 110547, i.e.5-phenoxy-1-[3-(trifluoromethyl)phenyl]-1H-tetrazole; UBH-509; D-489; LS82-556; KPP-300; KPP-421, MT-146, NC-324; KH-218; DPX-N8189; DOWCO-535;DK-8910; V-53482; PP-600; MBH-001.

[0281] For use, the formulations which are in commercially availableform are, if desired, diluted in the customary manner, for example usingwater in the case of wettable powders, emulsifiable concentrates,dispersions and water-dispersible granules. Preparations in the form ofdusts, soil granules, granules for broadcasting and sprayable solutionsare usually not diluted any further with other inert substances prior touse.

[0282] The necessary application rate of the herbicides of the formula(I) varies with the external conditions such as, inter alia,temperature, humidity, and the nature of the herbicide used. It may bevaried within wide limits, for example between 0.001 and 10.0 kg/ha ormore of active substance, but it is preferably between 0.005 and 5kg/ha.

[0283] The examples which follow serve to illustrate the invention:

[0284] A. Formulation Examples

[0285] a) A dust is obtained by mixing 10 parts by weight of a compoundof the formula (II)-(VII) and/or from group (b) or of an activesubstance mixture of a herbicidally active substance of the formula (I)and a safener of the formula (II)-(VII) and/or from group (b) and 90parts by weight of talc as inert substance and comminuting the mixturein a hammer mill.

[0286] b) A wettable powder which is readily dispersible in water isobtained by mixing 25 parts by weight of a compound of the formula (II),(III), (IV) and/or from group (b) or of an active substance mixture of aherbicidally active substance of the formula (I) and a safener of theformula (II), (III), (IV) and/or from group (b), 64 parts by weight ofkaolin-containing quartz as inert substance, 10 parts by weight ofpotassium lignosulfonate and 1 part by weight of sodiumoleoylmethyltaurinate as wetter and dispersant, and grinding the mixturein a pinned-disk mill.

[0287] c) A dispersion concentrate which is readily dispersible in wateris obtained by mixing 20 parts by weight of a compound of the formula(II)-(VII) and/or from group (b) or of an active substance mixture of aherbicidally active substance of the formula (I) and a safener of theformula (II)-(VII) and/or from group (b), 6 parts by weight ofalkylphenol polyglycol ether (®Triton X 207), 3 parts by weight ofisotridecanol polyglycol ether (8 EO) and 71 parts by weight ofparaffinic mineral oil (boiling range, for example, approx. 255 to above277° C.) and grinding the mixture in a ball mill to a fineness of below5 microns.

[0288] d) An emulsifiable concentrate is obtained from 15 parts byweight of a compound of the formula (II)-(VII) and/or from group (b) orof an active substance mixture of a herbicidally active substance of theformula (I) and a safener of the formula (II)-(VII) and/or from group(b), 75 parts by weight of cyclohexanone as solvent and 10 parts byweight of ethoxylated nonylphenol as emulsifier. e) Water-dispersiblegranules are obtained by mixing 75 parts by weight of a compound of theformula (II)-(VII) and/or from group (b) or of an active substancemixture of a herbicidally active substance of the formula (I) and asafener of the formula (II)-(VII) and/or from group (b) 10 parts byweight of calcium lignosulfonate,  5 parts by weight of sodium laurylsulfate,  3 parts by weight of polyvinyl alcohol and  7 parts by weightof kaolin, grinding the mixture on a pinned-disk mill and granulatingthe powder in a fluidized bed by spraying on water as granulationliquid. f) Water-dispersible granules are also obtained by homogenizingand precomminuting, in a colloid mill, 25 part(s) by weight of acompound of the formula (II)-(VII) and/or from groups (b) or of anactive substance mixture of a herbicidally active substance of theformula (I) and a safener of the formula (II)-(VII) and/or from group(b)  5 part(s) by weight of sodium 2,2′-dinaphthylmethane-6,6′-disulfonate  2 part(s) by weight of sodium oleoylmethyltaurinate,  1part(s) by weight of polyvinyl alcohol, 17 part(s) by weight of calciumcarbonate and 50 part(s) by weight of water, subsequently grinding themixture on a bead mill and atomizing and drying the resulting suspensionin a spray tower by means of a single-substance nozzle.

BIOLOGICAL EXAMPLES

[0289] 1. Damage Scoring

[0290] The damage to the plants is evaluated visually in comparison withcontrol plants, according to a scale from 0-100%:

[0291] 0%=no perceptible action in comparison with the untreated plant,

[0292] 100%=treated plant dies.

[0293] 2. Herbicide Action and Safener Action Preemergence

[0294] Seeds of monocotyledonous and dicotyledonous broadleaf weedplants and of crop plants are placed in sandy loam and plastic pots of 9cm in diameter and are covered with soil. Alternatively, for the testunder conditions for paddy rice, broadleaf weeds which occur in ricegrowing are cultivated in waterlog soil, the amount of water introducedinto the pots being such that the water comes up to the soil surface orseveral millimeters above it. The herbicide/safener active substancecombinations of the invention, formulated in the form of emulsifiableconcentrates, and, in parallel trials, the correspondingly formulatedindividual active substances, are then applied to the surface of thecovering earth or, in the case of rice, poured into the irrigation waterin the form of emulsions, at a water application rate of 300 l/ha(converted), at different concentrations.

[0295] Following treatment, the pots are placed in a greenhouse and arekept under good growth conditions. Visual scoring of the plant and/oremergence damage takes place after the trial plants have emerged, aftera trial period of 34 weeks, in comparison to untreated controls. As thetrials show, the herbicidal compositions of the invention have a goodpreemergence herbicidal action against a broad spectrum of gramineousand broadleaf weeds, with substantial reduction—that is, from around 50%up to 100% less herbicide damage—in damage to crop plants such as corn,rice, wheat or barley or other cereals in comparison with the use of theindividual herbicides without safeners.

[0296] 3. Herbicide Action and Safener Action Postemergence

[0297] Seeds of monocotyledonous and dicotyledenous broadleaf weedplants and of crop plants are placed in sandy loam and plastic pots,colored with soil and grown in a greenhouse under good growthconditions. Alternatively, for the test under conditions for paddy rice,broadleaf weeds that occur in rice growing, and rice, are cultivated inpots in which water stands up to 2 cm above the soil surface, and arecultivated during the growth phase. About three weeks after sowing, thetrial plants are treated at the three-leaf stage. The herbicide/safeneractive substance combinations of the invention, formulated asemulsifable or concentrates, and, in parallel trials, thecorrespondingly formulated individual active substances are sprayed onthe green parts of the plants at different concentrations with a waterapplication rate of 300 l/ha (converted) and, after the trial plantshave stood in the greenhouse for 3 weeks under optimum growthconditions, the action of the preparations is scored visually incomparison with untreated controls. In the case of rice or broadleafweeds which occur in rice growing, the active substances are alsointroduced directly into the irrigation water (application in analogy togranular application, as it is known) or on plants and sprayed into theirrigation water. In the case of field trials, seeds of monocotyledonousand dicotyledonous broadleaf weed plants and of crop plants were placedin sandy loam, covered with earth and grown. Further treatment was asdescribed above. Evaluation in the case took place two weeks after thetreatment with herbicide and/or safener. In the case of the trials withsugar cane, evaluation was carried out after 63 days. The experimentsshow that the herbicidal compositions of the invention exhibit a goodpostemergence herbicidal action against a broad spectrum of gramineousand broadleaf weeds, with substantial reduction—i.e., around 50% up to100% less herbicide damage—in damage to crop plants such as sugar cane,corn, rice, wheat or barley or other cereals in comparison with the useof the individual herbicides without safeners.

[0298] Table 1 specifies the herbicides used, and table 2 the safeners.Tables 3 to 7 indicate the percentage by which the damage in corn, sugarcane, rice, wheat or barley, respectively, caused by a herbicide islessened by simultaneous use of the safener. TABLE 1 Herbicides No.Structure H1

H2

H3

H4

H5

H6

H7

H8

[0299] TABLE 2 Safeners No. Structure S1

S2

S3

S4

S5

S6

S7

S8

S9

S10 

[0300] TABLE 3 Postemergence field trials, corn Compound No. Rate [g/ha]Reduction in damage to Herbicide Safener Herbicide Safener corn fromusing safener H1 S1 200 + 200  54% H1 S7 400 + 100  50% H2 S1 100 + 100100% H2 S1 200 + 100  96% H2 S7 80 + 80 100% H2 S8 80 + 80 100% H2 S980 + 80 100% H2 S10 80 + 80 100% H3 S1 150 + 150  84% H4 S1 150 + 150 89% H5 S1 150 + 150 100% H6 S1 150 + 150 100% H7 S1 150 + 150 100% H8S1 150 + 150  83%

[0301] TABLE 4 Postemergence field trials, sugar cane Reduction inCompound No. Rate [g/ha] damage to sugar cane Herbicide SafenerHerbicide Safener from using safener H2 S1 200 + 200 60%

[0302] TABLE 5 Postemergence greenhouse trials, rice Reduction inCompound No. Rate [g/ha] damage to rice Herbicide Safener HerbicideSafener from using safener H1 S1 100 + 200 78% H1 S3 120 + 600 68% H2 S2200 + 600 63% H8 S1 200 + 200 71%

[0303] TABLE 6 Postemergence greenhouse trials, wheat Reduction inCompound No. Rate [g/ha] damage to wheat Herbicide Safener HerbicideSafener from using safener H1 S4 20 + 80 21% H1 S5 20 + 80 29% H2 S4100 + 100 60% H2 S5 20 + 20 71% H2 S5 100 + 100 70% H2 S6 60 + 60 50%

[0304] TABLE 7 Postemergence greenhouse trials, barley Reduction inCompound No. Rate [g/ha] damage to barley Herbicide Safener HerbicideSafener from using safener H2 S5 180 + 180 100% H2 S5 100 + 100 100% H2S6 20 + 80  75%

[0305] In table 8, following the working examples, the seed was firsttreated with safener and, after sowing and emergence, the plant was thentreated with herbicide. Here again, a marked reduction in the damagecaused by the herbicide is evident in comparison to the seed which wasnot treated with safener. The amount of safener indicated is based onthe amount of seed. TABLE 8 Postemergence field trials following seedtreatment, corn Reduction in Compound No. Rate [g/ha] Rate [g/ha] damageto corn Herbicide Safener Herbicide Safener from using safener H2 S1 800.1 90% H2 S3 80 0.1 84% H2 S7 80 0.01 84% H2 S8 80 0.05 87%

What is claimed is:
 1. A herbicidal composition comprising B) aherbicidally effective amount of one or more compounds of the formula(I)

in which the symbols and indices have the following definitions: R¹ isnitro, amino, halogen, cyano, (C₁-C₄)-alkyl, (C₂-C₄)-alkenyl,(C₂-C₄)-alkynyl, (C₁-C₄)-haloalkyl, (C₂-C₄)-haloalkenyl,(C₂-C₄)-haloalkynyl, (C₁-C₄)-haloalkoxy, (C₁-C₄)-haloalkylthio,(C₁-C₄)-alkoxycarbonyl, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkylsulfinyl,(C₁-C₄)-alkylthio, (C₁-C₄)-alkoxy, (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy,(C₁-C₄)-alkylcarbonyl, (C₁-C₄)-alkylaminosulfonyl,(C₁-C₄)-dialkylaminosulfonyl, (C₁-C₄)-alkylcarbamoyl,(C₁-C₄)-dialkylcarbamoyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,(C₁-C₄)-alkylamino or (C₁-C₄)-dialkylamino; R² is(C₁-C₄)-haloalkoxy-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkoxy-(C₁-C₄)—alkoxy-(C₁-C₄)-alkyl, (C₃-C₆)-cycloalkoxy-(C₁-C₄)-alkyl,(C₃-C₆)-cycloalkyl-(C₁-C₄)-alkoxy,tetrahydrofuran-2-yl-methoxy-(C₁-C₄)-alkyl,tetrahydrofuran-3-yl-methoxy-(C₁-C₄)-alkyl or a heterocyclic radicalfrom the group consisting of isoxazol-3-yl and 4,5-dihydroisoxazol-3-ylwhich is substituted by a radical from the group consisting ofcyanomethyl, ethoxymethyl and methoxymethyl; R³ is OR⁵, cyano, halogen,cyanato, thiocyanato, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfinyl,(C₁-C₄)-alkylsulfonyl, (C₂-C₄)-alkenylthio, (C₂-C₄)-alkenylsulfinyl,(C₂-C₄)-alkenylsulfonyl, (C₂-C₄)-alkynylthio, (C₂-C₄)-alkynylsulfinyl,(C₂-C₄)-alkynylsulfonyl, (C₁-C₄)-haloalkylthio, (C₂-C₄)-haloalkenylthio,(C₂-C₄)-haloalkynylthio, (C₁-C₄)-haloalkylsulfinyl,(C₂-C₄)-haloalkenylsulfinyl, (C₂-C₄)-haloalkynylsulfinyl,(C₁-C₄)-haloalkylsulfonyl, (C₂-C₄)-haloalkenylsulfonyl or(C₂-C₄)-haloalkynylsulfonyl; R⁴ is (C₁-C₄)-alkyl; R⁵ is hydrogen,(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl or (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl; a is0, 1, 2 or 3; b is 0, 1 or 2; and B) an antidote-active amount of one ormore compounds from groups a) to e): b) compounds of the formula (II) to(IV),

in which the symbols and indices have the following definitions: n′ is anatural number from 1 to 5, preferably from 1 to 3; T is a (C₁- orC₂-)-alkanediyl chain which is unsubstituted or substituted by one ortwo (C₁-C₄)-alkyl radicals or by [(C₁-C₃)-alkoxy]carbonyl; W is aradical from the group (W1) to (W4),

m′ is 0 or 1; R¹⁷, R¹⁹ are identical or different and are hydrogen,halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro or (C₁-C₄)-haloalkyl; R¹⁸and R²⁰ are identical or different and are OR²⁴, SR²⁴ or NR²⁴R²⁵ or asaturated or unsaturated 3- to 7-membered heterocycle containing atleast one nitrogen atom and up to 3 heteroatoms which is bonded by thenitrogen atom to the carbonyl group in (II) or (III) and isunsubstituted or substituted by radicals from the group consisting of(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and unsubstituted or substituted phenyl,preferably a radical of the formula OR²⁴, NHR²⁵ or N(CH₃)₂, inparticular of the formula OR²⁴; R²⁴ is hydrogen or an unsubstituted orsubstituted aliphatic hydrocarbon radical, preferably having a total offrom 1 to 18 carbon atoms; R²⁵ is hydrogen, (C₁-C₆)-alkyl,(C₁-C₆)-alkoxy or substituted or unsubstituted phenyl; R²⁶ is hydrogen,(C₁-C₈)-alkyl, (C₁-C₈)-haloalkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,(C₁-C₆)-hydroxyalkyl, (C₃-C₁₂)-cycloalkyl or tri-(C₁-C₄)-alkylsilyl;R²⁷, R²⁸ and R²⁹ are identical or different and are hydrogen,(C₁-C₈)-alkyl, (C₁-C₆)-haloalkyl, (C₃-C₁₂)-cycloalkyl or substituted orunsubstituted phenyl; R²¹ is (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₂-C₄)-alkenyl, (C₂-C₄)-haloalkenyl, (C₃-C₇)-cycloalkyl, preferablydichloromethyl; R²², R²³ are identical or different and are hydrogen,(C₁-C₄)-alkyl, (C₂-C₄)-alkenyl, (C₂-C₄)-alkynyl, (C₁-C₄)-haloalkyl,(C₂-C₄)-haloalkenyl, (C₁-C₄)— alkylcarbamoyl-(C₁-C₄)-alkyl,(C₂-C₄)-alkenylcarbamoyl-(C₁-C₄)-alkyl, (C₁-C₄)-alkoxy-(C₁-C₄)-alkyl,dioxolanyl-(C₁-C₄)-alkyl, thiazolyl, furyl, furylalkyl, thienyl,piperidyl, substituted or unsubstituted phenyl, or R²² and R²³ togetherform a substituted or unsubstituted heterocyclic ring, preferably anoxazolidine, thiazolidine, piperidine, morpholine, hexahydropyrimidineor benzoxazine ring; c) one or more compounds from the following group:1,8-naphthalic anhydride, methyl diphenylmethoxyacetate,cyanomethoxyimino(phenyl)acetonitrile (cyometrinile),1,3-dioxolan-2-ylmethoxyimino(phenyl)acetonitrile (oxabetrinil),4′-chloro-2,2,2-trifluoroacetophenone O-1,3-dioxolan-2-ylmethyl oxime(fluxofenim), 4,6-dichloro-2-phenylpyrimidine (fenclorim), benzyl2-chloro-4-trifluoromethyl-1,3-thiazole-5-carboxylate (flurazole),2-dichloromethyl-2-methyl-1,3-dioxoiane (MG-191),N-(4-methylphenyl)-N′-(1-methyl-1-phenylethyl)urea (dymron),1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3-methylurea,1-[4-(N-2-methoxybenzoylsulfamoyl)phenyl]-3,3-dimethylurea,1-[4-(N-4,5-dimethylbenzoylsulfamoyl)phenyl]-3-methylurea,1-[4-(N-naphthoylsulfamoyl)phenyl]-3,3-dimethylurea,(2,4-dichlorophenoxy)acetic acid (2,4-D), (4-chlorophenoxy)acetic acid,(R,S)-2-(4-chloro-o-tolyloxy)propionic acid (mecoprop),4-(2,4-dichlorophenoxy)butyric acid (2,4-DB),(4-chloro-o-tolyloxy)acetic acid (MCPA), 4-(4-chloro-o-tolyloxy)butyricacid, 4-(4-chlorophenoxy)butyric acid, 3,6-dichloro-2-methoxybenzoicacid (dicamba), 1-(ethoxycarbonyl)ethyl 3,6-dichloro-2-methoxybenzoate(lactidichlor) and their salts and esters, preferably (C₁-C₈); c)N-acylsulfonamides of the formula (V) and their salts,

in which R³⁰ is hydrogen, a carbon-containing radical such as ahydrocarbon radical, a hydrocarbon-oxy radical, a hydrocarbon-thioradical or a heterocyclyl radical, each of the 4 last-mentioned radicalsbeing unsubstituted or being substituted by one or more identical ordifferent radicals selected from the group consisting of halogen, cyano,nitro, amino, hydroxyl, carboxyl, formyl, carboxamide, sulfonamide andradicals of the formula —Z^(a)—R^(a), each hydrocarbon moiety preferablyhaving 1 to 20 carbon atoms and a carbon-containing radical R³⁰inclusive of substituents preferably having 1 to 30 carbon atoms; R³¹ ishydrogen or (C₁-C₄)-alkyl, preferably hydrogen, or R³⁰ and R³¹ togetherwith the group of the formula —CO—N— are the residue of a 3- to8-membered saturated or unsaturated ring; R³² is identical or differentand is halogen, cyano, nitro, amino, hydroxyl, carboxyl, formyl, CONH₂,SO₂NH₂ or a radical of the formula —Z^(b)—R^(b); R³³ is hydrogen or(C₁-C₄)-alkyl, preferably H; R³⁴ is identical or different and ishalogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO, CONH₂, SO₂NH₂ ora radical of the formula —Z^(c)—R^(c); R^(a) is a hydrocarbon radical ora heterocyclyl radical, each of the two last-mentioned radicals beingunsubstituted or substituted by one or more identical or differentradicals selected from the group consisting of halogen, cyano, nitro,amino, hydroxyl, mono- and di-[(C₁-C₄)-alkyl]amino, or an alkyl radicalin which a plurality, preferably 2 or 3, non-adjacent CH₂ groups are ineach case replaced by one oxygen atom; R^(b),R^(c) are identical ordifferent and are a hydrocarbon radical or a heterocyclyl radical, eachof the two last-mentioned radicals being unsubstituted or substituted byone or more identical or different radicals selected from the groupconsisting of halogen, cyano, nitro, amino, hydroxyl, phosphoryl,halo-(C₁-C₄)-alkoxy, mono- and di-[(C₁-C₄)-alkyl]amino, or an alkylradical in which a plurality, preferably 2 or 3, non-adjacent CH₂ groupsare replaced in each case by one oxygen atom; Z^(a) is a divalent groupof the formula —O, —S, —CO, —CS, —CO—O, —CO—S, —O—CO, —S—CO, —SO, —SO₂,—NR*, —CO—NR*, —NR*—CO, —SO₂—NR* or —NR*—SO₂, the bond given on theright-hand side of each of the divalent groups being the bond to theradical R^(a), and the radicals R* in the 5 last-mentioned radicalsindependently of each other being in each case H, (C₁-C₄)-alkyl orhalo-(C₁-C₄)-alkyl; Z^(b),Z^(c) independently of one another are adirect bond or a divalent group of the formula —O, —S, —CO, —CS, —CO—O,—CO—S, —O—CO, —S—CO, —SO, —SO₂, —NR*, —SO₂—NR*, —NR*—SO₂, —CO—NR* or—NR*—CO, the bond given on the right-hand side to the radical R^(b) orR^(c) and the radicals R* in the 5 last-mentioned radicals independentlyof one another being in each case H, (C₁-C₄)-alkyl orhalo-(C₁-C₄)-alkyl; n is an integer from 0 to 4, preferably 0, 1 or 2,in particular 0 or 1, and m is an integer from 0 to 5, preferably 0, 1,2 or 3, in particular 0, 1 or 2; d) acylsulfamoylbenzamides of theformula (VI), optionally also in salt form,

in which X³ is CH or N; R³⁵ is hydrogen, heterocyclyl or a hydrocarbonradical, the two last-mentioned radicals optionally being substituted byone or more identical or different radicals selected from the groupconsisting of halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO,CONH₂, SO₂NH₂ and Z^(a)—R^(a); R³⁶ is hydrogen, hydroxyl, (C₁-C₆)-alkyl,(C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl, (C₁-C₆)-alkoxy, (C₂-C₆)-alkenyloxy,the five last-mentioned radicals optionally being substituted by one ormore identical or different radicals selected from the group consistingof halogen, hydroxyl, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy and(C₁-C₄)-alkylthio, or R³⁵ and R³⁶ together with the nitrogen atom towhich they are attached are a 3- to 8-membered saturated or unsaturatedring; R³⁷ is halogen, cyano, nitro, amino, hydroxyl, carboxyl, CHO,CONH₂, SO₂NH₂ or Z^(b)—R^(b); R³⁸ is hydrogen, (C₁-C₄)-alkyl,(C₂-C₄)-alkenyl or (C₂-C₄)-alkynyl; R³⁹ is halogen, cyano, nitro, amino,hydroxyl, carboxyl, phosphoryl, CHO, CONH₂, SO₂NH₂ or Z^(c)—R^(c); R^(a)is a (C₂-C₂₀)-alkyl radical whose carbon chain is interrupted once ormore than once by oxygen atoms, or is heterocyclyl or a hydrocarbonradical, the two last-mentioned radicals optionally being substituted byone or more identical or different radicals selected from the groupconsisting of halogen, cyano, nitro, amino, hydroxyl, mono- anddi-[(C₁-C₄)-alkyl]amino; R^(b), R^(c) are identical or different and area (C₂-C₂₀)-alkyl radical whose carbon chain is interrupted once or morethan once by oxygen atoms, or a heterocyclyl or a hydrocarbon radical,the two last-mentioned radicals optionally being substituted by one ormore identical or different radicals selected from the group consistingof halogen, cyano, nitro, amino, hydroxyl, phosphoryl,(C₁-C₄)-haloalkoxy, mono- and di-[(C₁-C₄)-alkyl]amino; Z^(a) is adivalent unit selected from the group consisting of O, S, CO, CS, C(O)O,C(O)S, SO, SO₂, NR^(d), C(O)NR^(d) or SO₂NR^(d); Z^(b), Z^(c) areidentical or different and are a direct bond or a divalent unit selectedfrom the group consisting of O, S, CO, CS, C(O)O, C(O)S, SO, SO₂,NR^(d), SO₂NR^(d) or C(O)NR^(d); R^(d) is hydrogen, (C₁-C₄)-alkyl or(C₁-C₄)-haloalkyl; r is an integer from 0 to 4, and q in the event thatX³ is CH, is an integer from 0 to 5 and, in the event that X is N, is aninteger from 0 to 4; f) compounds of the formula (VII),

in which the symbols and indices have the following definitions: X is CHor N, p in the event that X=N, is an integer from 0 to 2 and, in theevent that X=CH, is an integer from 0 to 3; R⁴⁰ is halogen,(C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy,nitro, (C₁-C₄)-alkylthio, (C₁-C₄)-alkylsulfonyl, (C₁-C₄)-alkoxycarbonyl,phenyl or phenoxy, the two last-mentioned radicals being unsubstitutedor substituted by one or more, preferably up to three, identical ordifferent radicals from the group consisting of halogen, (C₁-C₄)-alkyl,(C₁-C₄)-haloalkyl, (C₁-C₄)-alkoxy, halo-(C₁-C₄)-alkoxy, nitro and cyano;R⁴¹ is hydrogen or (C₁-C₄)-alkyl, and R⁴² is hydrogen, (C₁-C₈)-alkyl,(C₃-C₆)-cycloalkyl, (C₂-C₆)-alkenyl, (C₂-C₆)-alkynyl or aryl, each ofthe aforementioned carbon-containing radicals being unsubstituted orsubstituted by one or more, preferably up to three, identical ordifferent radicals from the group consisting of halogen, nitro, cyano,hydroxyl, (C₁-C₈)-alkoxy, in which one or more, preferably up to three,CH₂ groups may be replaced by oxygen, (C₁-C₄)-alkylthio,(C₁-C₄)-alkylsulfonyl, (C₃-C₆)-cycloalkyl, (C₂-C₄)-alkenyloxy and(C₂-C₄)-alkynyloxy, inclusive of the stereoisomers and theagriculturally customary salts.
 2. The herbicidal composition as claimedin claim 1, comprising safeners of the formula (II) and/or (III) whereinthe symbols and indices have the following definitions: R²⁴ is hydrogen,(C₁-C₁₈)-alkyl, (C₃-CO₂)-cycloalkyl, (C₂-C₈)-alkenyl and(C₂-C₈)-alkynyl, where the carbon-containing groups can be substitutedby one or more, preferably up to three, radicals R⁵⁰; R⁵⁰ is identicalor different and is halogen, hydroxyl, (C₁-C₈)-alkoxy,(C₁-C₈)-alkylthio, (C₂-C₈)-alkenylthio, (C₂-C₈)-alkynylthio,(C₂-C₈)-alkenyloxy, (C₂-C₈)-alkynyloxy, (C₃-C₇)-cycloalkyl,(C₃-C₇)-cycloalkoxy, cyano, mono- and di-(C₁-C₄)-alkyl)amino, carboxyl,(C₁-C₈)-alkoxycarbonyl, (C₂-C₈)-alkenyloxycarbonyl,(C₁-C₈)-alkylthiocarbonyl, (C₂-C₈)-alkynyloxycarbonyl,(C₁-C₈)-alkylcarbonyl, (C₂-C₈)-alkenylcarbonyl, (C₂-C₈)-alkynylcarbonyl,1-(hydroxyimino)-(C₁-C₆)-alkyl, 1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl,1-[(C₁-C₄)-alkoxyimino]-(C₁-C₆)-alkyl, (C₁-C₈)-alkylcarbonylamino,(C₂-C₈)-alkenylcarbonylamino, (C₂-C₈)-alkynylcarbonylamino,aminocarbonyl, (C₁-C₈)-alkylaminocarbonyl,di-(C₁-C₆)-alkylaminocarbonyl, (C₂-C₆)-alkenylaminocarbonyl,(C₂-C₆)-alkynylaminocarbonyl, (C₁-C₈)-alkoxycarbonylamino,(C₁-C₈)-alkylaminocarbonylamino, (C₁-C₆)-alkylcarbonyloxy which isunsubstituted or substituted by R⁵, or is (C₂-C₆)-alkenylcarbonyloxy,(C₂-C₆)-alkynylcarbonyloxy, (C₁-C₈)-alkylsulfonyl, phenyl,phenyl-(C₁-C₆)-alkoxy, phenyl-(C₁-C₆)-alkoxycarbonyl, phenoxy,phenoxy-(C₁-C₆)-alkoxy, phenoxy-(C₁-C₆)-alkoxycarbonyl,phenylcarbonyloxy, phenylcarbonylamino,phenyl-(C₁-C₆)-alkylcarbonylamino, for the phenyl ring being thelast-mentioned 9 radicals unsubstituted or mono- or polysubstituted,preferably up to trisubstituted, by radicals R⁵²; SiR′₃, OSiR′₃,R′₃Si—(C₁-C₈)-alkoxy, —CO—O—NR′₂, —O—N═CR′₂, —N═CR′₂, —O—NR′₂, —NR′₂,—CH(OR′)₂, —O—(CH₂)_(m)—CH(OR′)₂, —CR′″(OR′)₂, —O—(CH₂)_(m)CR′″(OR″)₂ orby R″O—CHR′″CHCOR″—(C₁-C₆)-alkoxy, R⁵¹ is identical or different and ishalogen, nitro, (C₁-C₄)-alkoxy and phenyl which is unsubstituted orsubstituted by one or more, preferably up to three, radicals R⁵¹; R⁵² isidentical or different and is halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy,(C₁-C₄)-haloalkyl, (C₁-C₄)-haloalkoxy or nitro; R′ is identical ordifferent and is hydrogen, (C₁-C₄)-alkyl, phenyl which is unsubstitutedor substituted by one or more, preferably up to three, radicals R⁵², ortwo radicals R′ together form a (C₂-C₆)-alkanediyl chain; R″ isidentical or different and is (C₁-C₄)-alkyl, or two radicals R″ togetherform a (C₂-C₆)-alkanediyl chain; R′″ is hydrogen or (C₁-C₄)-alkyl; m is0, 1, 2, 3, 4, 5 or
 6. 3. The herbicidal composition as claimed in claim1, comprising safeners of the formula (II) and/or (III) wherein thesymbols and indices have the following definitions: R²⁴ is hydrogen,(C₁-C₈)-alkyl or (C₃-C₇)-cycloalkyl, the above carbon-containingradicals being unsubstituted or mono- or polysubstituted by halogen ormono- or disubstituted, by preference monosubstituted, by radicals R⁵⁰,R⁵⁰ is identical or different and is hydroxyl, (C₁-C₄)-alkoxy, carboxyl,(C₁-C₄)-alkoxycarbonyl, (C₂-C₆)-alkenyloxycarbonyl,(C₂-C₆)-alkynyloxycarbonyl, 1-(hydroxyimino)-(C₁-C₄)-alkyl,1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl and1-[(C₁-C₄)-alkoxyimino]-(C₁-C₄)-alkyl; —SiR′₃, —O—N═CR′₂, —N═CR′₂, —NR′₂and ONR′₂ where R′ is identical or different and is hydrogen,(C₁-C₄)-alkyl or, as a pair, a (C₄-C₅)-alkanediyl chain, R²⁷, R²⁸, R²⁹are identical or different and are hydrogen, (C₁-C₈)-alkyl,(C₁-C₆)-haloalkyl, (C₃-C₇)-cycloalkyl or phenyl which is unsubstitutedor substituted by one or more radicals selected from the groupconsisting of halogen, cyano, nitro, amino, mono- anddi-[(C₁-C₄)-alkyl]amino, (C₁-C₄)-alkyl, (C₁-C₄)-haloalkyl,(C₁-C₄)-alkoxy, (C₁-C₄)-haloalkoxy, (C₁-C₄)-alkylthio and(C₁-C₄)-alkylsulfonyl; R¹⁷, R¹⁹ are identical or different and arehydrogen, halogen, methyl, ethyl, methoxy, ethoxy, (C₁ or C₂)-haloalkyl,by preference hydrogen, halogen or (C₁ or C₂)-haloalkyl.
 4. Theherbicidal composition as claimed in claim 1, comprising safeners of theformula (II) wherein the symbols and indices have the followingdefinitions: R¹⁷ is halogen, nitro or (C₁-C₄)-haloalkyl; n′ is 1, 2 or3; R¹⁸ is a radical of the formula OR²⁴; R²⁴ is hydrogen, (C₁-C₈)-alkylor (C₃-C₇)-cycloalkyl, where the above carbon-containing radicals areunsubstituted or mono- or polysubstituted, by preference up totrisubstituted, by identical or different halogen radicals or up todisubstituted, by preference monosubstituted, by identical or differentradicals selected from the group consisting of hydroxyl, (C₁-C₄)-alkoxy,(C₁-C₄)-alkoxycarbonyl, (C₂-C₆)-alkenyloxycarbonyl,(C₂-C₆)-alkynyloxycarbonyl, 1-(hydroxyimino)-(C₁-C₄)-alkyl,1-[(C₁-C₄)-alkylimino]-(C₁-C₄)-alkyl,1-[(C₁-C₄)-alkoxyimino]-(C₁-C₄)-alkyl and radicals of the formulae—SiR′₃, —O—N═R′₂, —N═CR′₂, —NR′₂ and —O—NR′₂, where the radicals R′ inthe above-mentioned formulae are identical or different and arehydrogen, (C₁-C₄)-alkyl or, as a pair, are (C₄ or C₅)-alkanediyl; R²⁷,R²⁸, R²⁹ are identical or different and are hydrogen, (C₁-C₈)-alkyl,(C₁-C₆)-haloalkyl, (C₃-C₇)-cycloalkyl or phenyl which is unsubstitutedor substituted by one or more of the radicals selected from the groupconsisting of halogen, (C₁-C₄)-alkyl, (C₁-C₄)-alkoxy, nitro,(C₁-C₄)-haloalkyl and (C₁-C₄)-haloalkoxy.
 5. The herbicidal compositionas claimed in claim 1, comprising compounds of the formula (I) whereinthe symbols and indices have the following definitions: R¹ is nitro,cyano, chlorine, fluorine, methyl, trifluoromethyl, methylsulfonyl orethylsulfonyl; R² is pentafluoroethoxymethyl, 2,2-difluoroethoxymethyl,2,2,2-trifluoroethoxymethyl, 2,2,3,3-tetrafluoropropoxymethyl,cyclopentyloxymethyl, cyclohexyloxymethyl, cyclopropyloxy,tetrahydrofuran-2-ylmethoxymethyl, methoxyethoxyethoxymethyl, or4,5-dihydroisoxazol-3-yl which is substituted by a radical from thegroup consisting of cyanomethyl, ethoxymethyl and methoxymethyl; R³ isOR⁵; R⁵ is hydrogen; a is 2; b is 0, and the two radicals R¹ are inpositions 2 and 4 of the phenyl ring.
 6. The herbicidal composition asclaimed in claim 1, wherein the ratio of herbicide to safener is from1:10 to 10:1.
 7. The herbicidal composition as claimed in claim 1,comprising a further herbicide.
 8. A method of controlling weed plantsin crops which comprises applying a herbicidally active amount of aherbicidal composition as claimed in claim 1 to the weed plants, plants,seeds of plants, or the area on which the plants are growing.
 9. Themethod as claimed in claim 8, wherein the plants are from the groupconsisting of sugar cane, corn, wheat, rye, barley, oats, rice, sorghum,cotton, and soya.
 10. The method as claimed in claim 8, wherein theplants have been genetically modified.